WO2023070401A1 - 电化学装置及包含该电化学装置的电子装置 - Google Patents

电化学装置及包含该电化学装置的电子装置 Download PDF

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WO2023070401A1
WO2023070401A1 PCT/CN2021/126833 CN2021126833W WO2023070401A1 WO 2023070401 A1 WO2023070401 A1 WO 2023070401A1 CN 2021126833 W CN2021126833 W CN 2021126833W WO 2023070401 A1 WO2023070401 A1 WO 2023070401A1
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active material
electrochemical device
electrode active
positive electrode
lithium
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French (fr)
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张洋洋
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Ningde Amperex Technology Ltd
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Ningde Amperex Technology Ltd
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Priority to PCT/CN2021/126833 priority Critical patent/WO2023070401A1/zh
Priority to EP21957734.3A priority patent/EP4207384A4/en
Priority to CN202180017516.5A priority patent/CN115191045B/zh
Priority to JP2023577477A priority patent/JP7715845B2/ja
Priority to KR1020237042756A priority patent/KR102909161B1/ko
Priority to US18/193,933 priority patent/US20240079635A1/en
Publication of WO2023070401A1 publication Critical patent/WO2023070401A1/zh
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0438—Processes of manufacture in general by electrochemical processing
    • H01M4/0459—Electrochemical doping, intercalation, occlusion or alloying
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/364—Composites as mixtures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/381—Alkaline or alkaline earth metals elements
    • H01M4/382—Lithium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M2010/4292—Aspects relating to capacity ratio of electrodes/electrolyte or anode/cathode
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present application relates to the field of electrochemistry, in particular to an electrochemical device and an electronic device including the electrochemical device.
  • lithium-ion batteries Due to the advantages of high energy storage density, high open circuit voltage, low self-discharge rate, long cycle life, and good safety performance, lithium-ion batteries are widely used in various fields such as electric energy storage, mobile electronic equipment, electric bicycles, electric vehicles, and aerospace equipment. field.
  • the performance of lithium-ion batteries mainly depends on the characteristics of the positive electrode, negative electrode, separator and electrolyte.
  • the positive active material in the positive electrode sheet is one of the important factors affecting the performance of lithium-ion batteries.
  • lithium manganese oxide as a commonly used positive electrode active material, is widely used in the fields of electric bicycles and electric vehicles.
  • the use of lithium manganate alone has the problems of poor high-temperature storage performance and short service life.
  • the purpose of the present application is to provide an electrochemical device and an electronic device including the electrochemical device, so as to improve the high-temperature storage performance and high-temperature cycle performance of the electrochemical device.
  • the first aspect of the present application provides an electrochemical device, which includes a positive electrode sheet and a negative electrode sheet, the negative electrode sheet includes a negative electrode active material layer, the negative electrode active material layer includes a negative electrode active material, and the positive electrode sheet includes Positive electrode active material layer, positive electrode active material layer comprises positive electrode active material, positive electrode active material comprises lithium manganese oxide;
  • the lattice parameter of lithium manganese oxide For example, the lattice parameter a of lithium manganese oxide is Or any value between any two value ranges above.
  • the lattice parameter a of the lithium manganese oxide is regulated within the above range, which can make the lithium manganese oxide within the entire SOC variation range of the electrochemical device (ie 0% SOC to 100% SOC range) can maintain a stable crystal structure, thereby improving the high-temperature cycle performance of the electrochemical device.
  • it can also reduce the structural distortion of lithium manganese oxide during the charge-discharge cycle of the electrochemical device, inhibit the dissolution of Mn (manganese) ions, make the distribution of Mn on the negative electrode more uniform, and reduce the impact on the SEI (solid electrolyte interface) film on the negative electrode. destruction, thereby improving the high-temperature storage performance of electrochemical devices.
  • it can also improve the lithium separation at the negative electrode and improve the safety performance of the electrochemical device.
  • the lithium manganese oxide includes Li x Mn 2-y M y O 4 , wherein, 0.9 ⁇ x ⁇ 1.1, 0 ⁇ y ⁇ 0.05, M includes Al, Mg, Ti, Cr, Cu , Fe, Co, W, Zn, Ga, Zr, Ru, Ag, Sn, Au, La, Ce, Pr, Nd, Sm, Nb or Gd at least one.
  • the positive electrode active material further includes at least one of a lithium transition metal composite oxide or a lithium transition metal phosphate compound.
  • the lithium transition metal composite oxide includes Li x1 Ni y1 Co z1 Mnk Z q O 2 ⁇ a T a , wherein Z includes B, Mg, Al, Si, P, S , at least one of Ti, Cr, Fe, Cu, Zn, Ga, Y, Zr, Mo, Ag, W, In, Sn, Pb, Sb or Ce, T is halogen; where, 0.2 ⁇ x1 ⁇ 1.2, 0 ⁇ y1 ⁇ 1, 0 ⁇ z1 ⁇ 1, 0 ⁇ k ⁇ 1, 0 ⁇ q ⁇ 1, and y1, z1, k are not 0 at the same time, and 0 ⁇ a ⁇ 1;
  • the lithium transition metal phosphate compound includes Li x2 R y2 N z2 PO 4 , wherein R includes at least one of Fe or Mn; N includes Al, Ti, V, Cr, Co , Li, Ni, Cu, Zn, Mg, Ga, Zr, Nb or Si; wherein, 0.6 ⁇ x2 ⁇ 1.2, 0.95 ⁇ y2 ⁇ 1, 0 ⁇ z2 ⁇ 0.05.
  • the mass percentage W1 of Mn in the positive electrode active material is 42% to 47%.
  • the mass percentage of Mn is 42%, 42.3%, 46.9%, 47%, or any value between any two value ranges above.
  • the mass percentage W1 of Mn in the positive electrode active material is regulated within the above range, and the proportion of lithium manganate in the positive electrode active material is appropriate, which can reduce the influence of the poor high-temperature storage performance of the lithium manganate material itself, and ensure The improvement effect of other active materials on the dissolution of Mn can inhibit the dissolution of Mn and its deposition on the negative electrode, thereby improving the high-temperature cycle performance of the electrochemical device; at the same time, it can further improve the low-temperature discharge performance of the electrochemical device.
  • the mass percentage W2 of Mn in the negative electrode active material is less than or equal to 0.1%.
  • the mass percentage of Mn is 0.0050%, 0.0100%, 0.0150%, 0.0201%, 0.0230%, 0.0265%, 0.0280%, 0.0294%, 0.0300%, 0.0320%, 0.0340%, 0.0350% %, 0.0450%, 0.0550%, 0.0650%, 0.0750%, 0.0850%, 0.0950%, 0.1%, or any value between any two of the above ranges.
  • the mass percentage W2 of Mn in the negative electrode active material is less than or equal to 0.1%, which can reduce the risk of destroying the stability of the negative electrode SEI film, thereby improving the high temperature storage performance of the electrochemical device.
  • the negative electrode sheet includes a first region, a second region, and a third region between the first region and the second region, based on the quality of the negative active material in the first region, the first The mass percentage composition V1 of Mn in the region; Based on the quality of the negative electrode active material in the second region, the mass percent composition V2 of Mn in the second region; Based on the quality of the negative electrode active material in the 3rd region, the Mn in the 3rd region The mass percentage V3; the difference between the maximum value and the minimum value in V1, V2 and V3 is ⁇ V, and the average value of V1, V2 and V3 is V, satisfying: ⁇ V/V ⁇ 20%.
  • the value of ⁇ V/V can be 0%, 1.45%, 3%, 4%, 5%, 7.8%, 9.2%, 10.4%, 10.5%, 10.8%, 11%, 11.5%, 11.8%, 11.9% , 12.1%, 12.3%, 12.4%, 12.5%, 13%, 17%, 19%, 20%, or any value between any two value ranges above.
  • the adjustment of ⁇ V/V value within the above range can reduce the difference of Mn distribution in the negative electrode sheet, and the uniform distribution of Mn can make the difference in the kinetics and stability of the negative electrode surface small, reduce the negative electrode side reaction and lithium precipitation risk, and improve the high-temperature service life and safety and reliability of electrochemical devices.
  • the first area includes the first side of the negative pole piece in the width direction to the area where the distance from the first side is 10mm, and the first side is provided with tabs;
  • the second area includes the negative pole piece in the width direction. The distance from the second side in the direction to the second side is 10 mm, and the second side is opposite to the first side.
  • the mass percentage content V1 of Mn in the first area is 0.1020% to 0.1100%.
  • the mass percentage V2 of Mn in the second region is 0.0950% to 0.1000%.
  • the mass percent content V3 of Mn in the third region is 0.1020% to 0.1100%.
  • the lithium manganese oxide includes a doping element M
  • the doping element M includes at least one of Nb, Al, Mg, Ti, Cr, Mo, Zr, Y or B
  • the lithium manganese oxide The mole percentage of the doping element M and Mn in the compound is 0.01% to 2%.
  • the molar percentage of the doping elements M and Mn in the lithium manganese oxide is 0.014%, 0.42%, 0.70%, 1.39%, 1.74%, or any value between any two value ranges above.
  • the molar percentage of the doping element M and Mn in the lithium manganese oxide is too large (for example, greater than 2%), the high-temperature cycle performance and high-temperature storage performance of the electrochemical device may no longer be significantly improved, and there will be a decrease The risk of electrochemical device capacity; the molar percentage of the doping element M and Mn in the lithium manganese oxide is too small (for example, less than 0.01%), and the improvement effect on the high-temperature cycle performance and high-temperature storage performance of the electrochemical device may not be obvious.
  • the particle density of the lithium manganese oxide increases, the ratio of Mn 3+ /Mn 4+ in the lithium manganese oxide decreases, and the lithium manganese oxide
  • the structural stability of the oxide is improved, which can effectively improve the Mn deposition amount of the negative electrode, thereby improving the high-temperature storage performance and high-temperature cycle performance of the electrochemical device.
  • the particle size distribution of the positive electrode active material satisfies: 1.2 ⁇ (Dv90 ⁇ Dv10)/Dv50 ⁇ 2.2.
  • the value of (Dv90 ⁇ Dv10)/Dv50 is 1.2, 1.32, 1.48, 2.2 or any value between any two value ranges mentioned above.
  • the particle distribution range of the positive electrode active material will be wider, which is more conducive to the reasonable combination of large particle size particles and small particle size particles.
  • the pressure and fragmentation degree of the positive electrode material particles are reduced, which is more conducive to reducing the Mn dissolution of the positive electrode, improving the Mn deposition amount of the negative electrode and the uniformity of the Mn distribution of the negative electrode sheet, thereby improving the high temperature storage performance of the electrochemical device. And high temperature cycle performance can be further improved.
  • the present application has no special limitation on the Dv10, Dv50 and Dv90 of the positive electrode active material, as long as the purpose of the present application can be achieved.
  • the Dv10 of the cathode active material is 0.9 ⁇ m to 6 ⁇ m.
  • the Dv50 of the positive electrode active material is 9 ⁇ m to 18 ⁇ m.
  • the Dv90 of the positive electrode active material is 19 ⁇ m to 35 ⁇ m.
  • Dv10 means the particle diameter at which the particles reach 10% of volume accumulation from the small particle diameter side in the volume-based particle size distribution.
  • Dv50 indicates the particle diameter at which the particles reach 50% of volume accumulation from the small particle diameter side in the volume-based particle size distribution.
  • Dv90 indicates the particle diameter at which the particles reach 90% of volume accumulation from the small particle diameter side in the volume-based particle size distribution.
  • the SOC of the electrochemical device is 0%, the potential of the negative electrode plate to Li is less than 0.6V, the side reactions at the negative electrode interface of the electrochemical device at high temperature are reduced, and the high-temperature cycle performance and service life of the electrochemical device are improved.
  • the positive electrode active material layer has a compacted density of 2.8 g/cm 3 to 3.05 g/cm 3 .
  • the compacted density of the positive electrode active material layer is 2.8 g/cm 3 , 2.95 g/cm 3 , 3.05 g/cm 3 or any value between any two value ranges mentioned above.
  • the compaction density of the positive electrode active material layer is regulated within the above range, the risk of particle breakage of the positive electrode active material is reduced, the dissolution of Mn can be suppressed, and the interfacial stability of the positive electrode active material layer can be improved; at the same time, the positive electrode active material particles
  • the contact is better, which is conducive to improving the conductivity of the conductive network, better regulating the dissolution of Mn and the interfacial stability of the positive electrode active material layer, which is more conducive to improving the high-temperature storage performance and high-temperature cycle performance of the electrochemical device.
  • the negative electrode active material layer has a compacted density of 1.45 g/cm 3 to 1.65 g/cm 3 .
  • the compacted density of the negative electrode active material layer is 1.45 g/cm 3 , 1.55 g/cm 3 , 1.65 g/cm 3 or any value between any two value ranges mentioned above.
  • the compaction density of the negative electrode active material layer is adjusted within the above range, the risk of particle breakage of the negative electrode active material is reduced, and at the same time, it is more conducive to regulating the deposition amount and distribution uniformity of the Mn dissolved from the positive electrode on the negative electrode, thereby It is more conducive to improving the high-temperature storage performance and high-temperature cycle performance of the electrochemical device.
  • the porosity ⁇ of the positive electrode active material layer is 15% to 40%.
  • the porosity ⁇ is 15%, 20%, 25%, 30%, 35%, 40%, or any value between any two value ranges mentioned above.
  • the control of porosity ⁇ within the above range can suppress the contact failure between the positive electrode active material particles in the electrochemical device during the charge-discharge cycle, resulting in a decrease in the cycle performance and energy density of the electrochemical device; at the same time, it can Ensure that the positive electrode active material is fully infiltrated by the electrolyte, reduce the transmission distance of lithium ions, and improve the kinetic performance of the electrochemical device.
  • the porosity ⁇ of the positive electrode active material layer refers to the percentage of the volume of pores between components in the positive electrode active material layer to the apparent volume of the positive electrode active material layer.
  • the starting position of the exothermic peak on the DSC (differential scanning calorimetry) curve of the positive pole piece is between 260°C and 280°C . It shows that the electrochemical device has good thermal stability, so it has good high-temperature storage performance, high-temperature cycle performance and safety performance.
  • the electrochemical device also includes an electrolyte, which includes a compound containing a sulfur-oxygen double bond; based on the quality of the electrolyte, the mass percentage of the compound containing a sulfur-oxygen double bond is 0.01% to 1.00%.
  • the mass percentage of the compound containing sulfur-oxygen double bonds is 0.01%, 0.50%, 1.00%, or any value between any two value ranges above.
  • by adjusting the mass percentage of the compound containing sulfur-oxygen double bonds within the above range it is more conducive to further improving the high-temperature storage performance and high-temperature cycle performance of the electrochemical device, thereby further balancing the electrochemical device. Comprehensive performance.
  • the present application has no particular limitation on the types of compounds containing sulfur-oxygen double bonds, as long as the purpose of the present application can be achieved.
  • the compound containing a sulfur-oxygen double bond may include at least one of 1,3-propane sultone or vinyl sulfate.
  • the electrolytic solution of the present application also includes a lithium salt and a non-aqueous solvent.
  • the present application has no particular limitation on the type of lithium salt, as long as the purpose of the present application can be achieved.
  • the lithium salt may include at least one of lithium hexafluorophosphate (LiPF 6 ), LiCH 3 SO 3 , LiCF 3 SO 3 , LiN(SO 2 CF 3 ) 2 , LiC(SO 2 CF 3 ) 3 , or LiSiF 6 .
  • LiPF 6 may be included because LiPF 6 can give high ion conductivity and improve high temperature cycle performance of lithium ion batteries.
  • the present application has no special limitation on the non-aqueous solvent, as long as the purpose of the present application can be achieved.
  • the nonaqueous solvent may contain at least one of carbonate compounds, carboxylate compounds, ether compounds, or other organic solvents.
  • the above-mentioned carbonate compound may be at least one of a chain carbonate compound or a cyclic carbonate compound.
  • Above-mentioned chain carbonate compound can comprise dimethyl carbonate (DMC), diethyl carbonate (DEC), dipropyl carbonate (DPC), methyl propyl carbonate (MPC), ethylene propyl carbonate (EPC) or methyl carbonate At least one of ethyl ester (MEC).
  • the cyclic carbonate compound may include at least one of ethylene carbonate (EC), propylene carbonate (PC), or butylene carbonate (BC).
  • the above carboxylate compound may include at least one of ethyl acetate, n-propyl acetate, tert-butyl acetate, methyl propionate, ethyl propionate, or propyl propionate.
  • the aforementioned ether compounds may include dibutyl ether, tetraglyme, diglyme, 1,2-dimethoxyethane, 1,2-diethoxyethane, ethoxymethoxy at least one of ethyl ethane, 2-methyltetrahydrofuran or tetrahydrofuran.
  • the above-mentioned other organic solvents may include dimethyl sulfoxide, 1,2-dioxolane, sulfolane, methyl sulfolane, 1,3-dimethyl-2-imidazolidinone, N-methyl-2-pyrrolidone, methyl At least one of amide, dimethylformamide, acetonitrile, trimethyl phosphate, triethyl phosphate, trioctyl phosphate or phosphoric acid ester.
  • negative electrode active materials can include natural graphite, artificial graphite, mesophase microcarbon spheres (MCMB), hard carbon, soft carbon, silicon, silicon-carbon composites, SiOx (0 ⁇ x ⁇ 2), Li-Sn alloy , Li-Sn-O alloy, Sn, SnO, SnO 2 , lithium titanate Li 4 Ti 5 O 12 with spinel structure, Li-Al alloy or metal lithium.
  • MCMB mesophase microcarbon spheres
  • the negative electrode sheet of the present application also includes a negative electrode collector.
  • the present application has no particular limitation on the negative electrode collector, as long as the purpose of the present application can be achieved.
  • the negative electrode current collector may include copper foil, copper alloy foil, nickel foil, stainless steel foil, titanium foil, nickel foam, copper foam, or a composite current collector.
  • the thickness of the negative electrode current collector and the negative electrode active material layer there is no particular limitation on the thickness of the negative electrode current collector and the negative electrode active material layer, as long as the purpose of the present application can be achieved.
  • the thickness of the negative electrode current collector is 6 ⁇ m to 10 ⁇ m
  • the thickness of the single-sided negative electrode active material layer is 30 ⁇ m to 130 ⁇ m.
  • the negative electrode active material layer may be disposed on one surface in the thickness direction of the negative electrode current collector, or may be disposed on two surfaces in the thickness direction of the negative electrode current collector. It should be noted that the "surface" here may be the entire area of the negative electrode collector, or a partial area of the negative electrode collector. This application is not particularly limited, as long as the purpose of this application can be achieved.
  • the negative electrode sheet may further include a conductive layer, and the conductive layer is located between the negative electrode current collector and the negative electrode active material layer.
  • the present application has no particular limitation on the composition of the conductive layer, which may be a commonly used conductive layer in the field.
  • the conductive layer includes a conductive agent and a binder.
  • the positive pole piece of the present application also includes a positive current collector.
  • the present application has no special limitation on the positive electrode current collector, as long as the purpose of the present application can be achieved.
  • the positive electrode current collector may include aluminum foil, aluminum alloy foil, or a composite current collector.
  • the thickness of the positive electrode collector is 5 ⁇ m to 20 ⁇ m, preferably 6 ⁇ m to 18 ⁇ m.
  • the thickness of the positive electrode active material layer on one side is 30 ⁇ m to 120 ⁇ m.
  • the positive electrode active material layer may be disposed on one surface in the thickness direction of the positive electrode current collector, or may be disposed on two surfaces in the thickness direction of the positive electrode current collector. It should be noted that the "surface" here may refer to the entire area of the positive electrode collector or a partial area of the positive electrode collector. This application is not particularly limited, as long as the purpose of this application can be achieved.
  • the positive electrode sheet may further include a conductive layer, and the conductive layer is located between the positive electrode current collector and the positive electrode active material layer.
  • the present application has no particular limitation on the composition of the conductive layer, which may be a commonly used conductive layer in the field.
  • the conductive layer includes a conductive agent and a binder.
  • the present application has no special limitation on the above-mentioned conductive agent and binder, as long as the purpose of the present application can be achieved.
  • the conductive agent can include at least one of conductive carbon black (Super P), carbon nanotubes (CNTs), carbon nanofibers, flake graphite, acetylene black, carbon black, Ketjen black, carbon dots, carbon nanotubes or graphene A sort of.
  • the binder may include polyacryl alcohol, sodium polyacrylate, potassium polyacrylate, lithium polyacrylate, polyimide, polyimide, polyamideimide, styrene-butadiene rubber (SBR), polyvinyl alcohol ( PVA), polyvinylidene fluoride, polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), polyvinyl butyral (PVB), water-based acrylic resin, carboxymethyl cellulose (CMC) or carboxymethyl At least one of sodium cellulose base (CMC-Na).
  • SBR styrene-butadiene rubber
  • PVA polyvinyl alcohol
  • PVDF polyvinylidene fluoride
  • PVDF polyvinylidene fluoride
  • PTFE polytetrafluoroethylene
  • PVB polyvinyl butyral
  • water-based acrylic resin carboxymethyl cellulose (CMC) or carboxymethyl At least one of sodium cellulose base (CMC-Na).
  • the electrochemical device of the present application also includes a diaphragm, which is used to separate the positive pole piece and the negative pole piece, prevent the internal short circuit of the lithium ion battery, allow the electrolyte ions to pass through freely, and complete the electrochemical charge and discharge process.
  • the separator in the present application is not particularly limited, as long as the purpose of the present application can be achieved.
  • polyethylene (PE), polypropylene (PP)-based polyolefin (PO)-based separators polyester films (such as polyethylene terephthalate (PET) films), cellulose films, polyimide films, etc.
  • a separator may include a substrate layer and a surface treatment layer.
  • the substrate layer can be a non-woven fabric, a film or a composite film with a porous structure, and the material of the substrate layer can include at least one of polyethylene, polypropylene, polyethylene terephthalate or polyimide .
  • a polypropylene porous film, a polyethylene porous film, a polypropylene non-woven fabric, a polyethylene non-woven fabric, or a polypropylene-polyethylene-polypropylene porous composite film may be used.
  • at least one surface of the substrate layer is provided with a surface treatment layer, and the surface treatment layer may be a polymer layer or an inorganic layer, or a layer formed by mixing a polymer and an inorganic material.
  • the inorganic layer includes inorganic particles and a binder
  • the inorganic particles are not particularly limited, for example, they can be selected from aluminum oxide, silicon oxide, magnesium oxide, titanium oxide, hafnium oxide, tin oxide, cerium oxide, nickel oxide , at least one of zinc oxide, calcium oxide, zirconia, yttrium oxide, silicon carbide, boehmite, aluminum hydroxide, magnesium hydroxide, calcium hydroxide or barium sulfate.
  • the binder is not particularly limited, for example, it can be selected from polyvinylidene fluoride, a copolymer of vinylidene fluoride-hexafluoropropylene, polyamide, polyacrylonitrile, polyacrylate, polyacrylic acid, polyacrylate, polyvinyl pyrene At least one of rolidone, polyvinyl ether, polymethylmethacrylate, polytetrafluoroethylene or polyhexafluoropropylene.
  • the polymer layer comprises a polymer, and the polymer material includes polyamide, polyacrylonitrile, acrylate polymer, polyacrylic acid, polyacrylate, polyvinylpyrrolidone, polyvinyl ether, polyvinylidene fluoride or poly( at least one of vinylidene fluoride-hexafluoropropylene).
  • the electrochemical device of the present application is not particularly limited, and it may include any device that undergoes an electrochemical reaction.
  • the electrochemical device may include, but is not limited to, a lithium metal secondary battery, a lithium ion secondary battery, a lithium polymer secondary battery, or a lithium ion polymer secondary battery, and the like.
  • the preparation process of electrochemical devices is well known to those skilled in the art, and the present application is not particularly limited.
  • it may include but not limited to the following steps: stack the positive pole piece, separator and negative pole piece in order, and place the The electrode assembly with winding structure is obtained by winding, folding and other operations, the electrode assembly is put into the packaging case, the electrolyte is injected into the packaging case and sealed to obtain an electrochemical device; or, the positive electrode sheet, separator and negative electrode sheet Stack in order, and then fix the four corners of the entire laminated structure with adhesive tape to obtain the electrode assembly of the laminated structure, put the electrode assembly into the packaging case, inject the electrolyte into the packaging case and seal it, and obtain the electrochemical device.
  • anti-overcurrent elements, guide plates, etc. can also be placed in the packaging case as needed, so as to prevent pressure rise and overcharge and discharge inside the electrochemical device.
  • the second aspect of the present application provides an electronic device, including the electrochemical device described in any one of the foregoing solutions of the present application.
  • the electronic device has good high-temperature storage performance and high-temperature cycle performance.
  • the electronic devices of the present application are not particularly limited, and may include but not limited to the following types: notebook computers, pen-input computers, mobile computers, e-book players, portable phones, portable fax machines, portable copiers, portable printers, head-mounted Stereo headphones, VCRs, LCD TVs, portable cleaners, portable CD players, mini-discs, transceivers, electronic organizers, calculators, memory cards, portable tape recorders, radios, backup power supplies, electric motors, automobiles, motorcycles, power-assisted bicycles , bicycles, lighting appliances, toys, game consoles, clocks, electric tools, flashlights, cameras, large household batteries and lithium-ion capacitors, etc.
  • the present application provides an electrochemical device and an electronic device comprising the electrochemical device, the electrochemical device includes a negative electrode sheet and a positive electrode sheet, the negative electrode sheet includes a negative electrode active material layer, and the negative electrode active material layer includes a negative electrode active material,
  • the present application is explained by taking the lithium-ion battery as an example of the electrochemical device, but the electrochemical device of the present application is not limited to the lithium-ion battery.
  • the positive electrode active material powder is obtained for future use. Take 6 parallel samples of the processed positive electrode active material powder, weigh, digest and dilute respectively, and then use the inductively coupled plasma emission spectrometer of the Thermo ICAP6300 model to test the mass percentages of different elements and calculate the average value.
  • the mass percentage content of the element is the mass percentage content in the positive electrode active material.
  • the lithium-ion battery Fully charge the lithium-ion battery to 2.8V, disassemble the negative pole piece, soak it in DMC solution for 24 hours, dry it for later use; divide the pole piece into three areas along the width direction of the pole piece, the first area is close to the pole piece The area of 10mm from the edge of the ear side to the center of the pole piece, the second area is the area of 10mm from the edge of the non-ear side to the center of the pole piece, and the third area is the remaining part of the pole piece; in the first area of the processed negative pole piece, The second area and the third area take 6 parallel samples respectively, weigh, digest and dilute respectively, then use the inductively coupled plasma emission spectrometer of Thermo ICAP6300 model to test the mass percentage content of Mn element, and calculate the average value, the measured The mean values of the mass percentages of Mn in the first area, the second area, and the third area are obtained as V1, V2, and V3, respectively. Define the Mn content V of the negative electrode as the average value of V
  • the Dv10, Dv50 and Dv90 of the positive electrode active material were tested using a laser particle size analyzer.
  • mc is the mass of the positive electrode active material layer, unit: g
  • Vc is the volume of the positive electrode active material layer, unit: cm 3 , wherein, the volume Vc is the difference between the area Sc of the positive electrode active material layer and the thickness of the positive electrode active material layer product.
  • ma is the mass of the negative electrode active material layer, unit: g;
  • Va is the volume of the negative electrode active material layer, unit: cm 3 , wherein, the volume Va is the difference between the area Sa of the negative electrode active material layer and the thickness of the negative electrode active material layer product.
  • the positive electrode active material layer on the surface of the positive electrode sheet was cleaned, and the thickness of the current collector was measured as h2 with a micrometer, and the apparent volume of the positive electrode active material layer ⁇ d 2 ⁇ (h1-h2) was calculated.
  • DSC is used to measure the relationship between the heat flow difference and temperature of the sample and reference.
  • STA449F3 model synchronous thermal analyzer to test the DSC curve.
  • the range is 150°C to 400°C
  • the heating rate is 10°C/min
  • the DSC curve is obtained.
  • the lithium-ion battery was subjected to constant current at a charging current of 0.5C until the upper limit voltage was 4.2V, and then was discharged at a constant current of 1C until the final voltage was 2.8V, recording the first time cycle discharge capacity. Then perform 500 charge and discharge cycles in the same steps, and record the discharge capacity of the 500th cycle lithium-ion battery.
  • the cycle capacity retention rate (%) of the lithium ion battery (discharge capacity of the 500th cycle/discharge capacity of the first cycle) ⁇ 100%.
  • Each embodiment or comparative example tests 4 samples, gets average value.
  • the high-temperature storage capacity retention rate (%) of the lithium-ion battery capacity after storage/capacity before storage ⁇ 100%.
  • the raw materials lithium carbonate and manganese dioxide are mixed according to the Li:Mn molar ratio of 0.545:1, and a certain amount of niobium pentoxide (Nb 2 O 5 ) is added as an additive to make the molar percentage of Nb and Mn in lithium manganese oxide 0.42%, the reaction produces lithium manganese oxide.
  • niobium pentoxide Nb 2 O 5
  • the above lithium manganese oxide and layered lithium nickel cobalt manganese oxide Li(Ni 0.55 Co 0.15 Mn 0.30 )O 2 are mixed according to a mass ratio of 80:20 to obtain a positive electrode active material.
  • the above steps are repeated on the other surface of the positive electrode sheet to obtain a positive electrode sheet coated with a positive electrode active material layer on both sides.
  • Negative electrode active material artificial graphite, conductive agent acetylene black, binder SBR, and thickener sodium carboxymethylcellulose were mixed according to a mass ratio of 95:2:2:1, and then deionized water was added to prepare a solid content of 70 % negative electrode slurry, and stirred under the action of a vacuum mixer until the system becomes a uniform negative electrode slurry.
  • the negative electrode slurry was uniformly coated on one surface of the negative electrode current collector copper foil with a thickness of 8 ⁇ m, and dried at 90° C. to obtain a negative electrode sheet with a coating thickness of 130 ⁇ m and a negative electrode active material layer coated on one side.
  • the above steps are repeated on the other surface of the negative electrode to obtain a negative electrode sheet coated with negative electrode active material layers on both sides. After drying at 90°C, cold pressing with a compaction density of 1.55g/cm 3 , and then cutting into pieces and welding tabs to obtain negative pole pieces.
  • a PE porous polymer film with a thickness of 14 ⁇ m was used.
  • the positive pole piece, separator, and negative pole piece prepared above are stacked in order, so that the separator is placed between the positive pole piece and the negative pole piece to play the role of isolation, and then wound to obtain an electrode assembly.
  • Put the electrode assembly into an aluminum-plastic film packaging case place it in a vacuum oven at 85°C to dry for 12 hours to remove moisture, inject the above-mentioned prepared electrolyte, and obtain lithium after vacuum packaging, standing, chemical formation, degassing, and shaping. ion battery.
  • Example 1-2 except that during the preparation of lithium manganese oxide, the Li:Mn molar ratio of the raw materials lithium carbonate and manganese dioxide is 0.560:1, the rest are the same as in Example 1-1.
  • Example 1-3 in addition to lithium manganese oxide, lithium iron phosphate LiFePO 4 and layered nickel cobalt lithium manganese oxide Li (Ni 0.55 Co 0.15 Mn 0.30 ) O 2 are mixed according to the mass ratio of 80:15:5 as the positive electrode active material , all the other are identical with embodiment 1-2.
  • lithium iron phosphate LiFePO 4 and layered nickel cobalt lithium manganese oxide Li (Ni 0.55 Co 0.15 Mn 0.30 ) O 2 are mixed according to the mass ratio of 80:10:10 as the positive electrode active material , all the other are identical with embodiment 1-3.
  • Example 1-5 except that in the preparation process of lithium manganese oxide, the Li:Mn molar ratio of the raw materials lithium carbonate and manganese dioxide is 0.575:1, the rest is the same as that of Example 1-4.
  • Example 1-6 except that in the preparation process of lithium manganese oxide, the Li:Mn molar ratio of the raw materials lithium carbonate and manganese dioxide is 0.575:1, the rest is the same as that of Example 1-1.
  • Example 1-7 except that in the preparation process of lithium manganese oxide, the Li:Mn molar ratio of the raw materials lithium carbonate and manganese dioxide is 0.580:1, the rest is the same as that of Example 1-1.
  • Example 1-8 except that in the preparation process of lithium manganese oxide, the Li:Mn molar ratio of the raw materials lithium carbonate and manganese dioxide is 0.580:1, the rest are the same as in Example 1-5.
  • Example 2-1 except that there is no niobium pentoxide additive in the preparation process of lithium manganese oxide, the rest is the same as that of Example 1-2.
  • Example 2-2 except that magnesium oxide (MgO) is used as an additive in the preparation process of the lithium manganese oxide, so that the molar percentage of Mg and Mn in the lithium manganese oxide is 0.42%, the rest is the same as that of Example 1-2.
  • MgO magnesium oxide
  • Example 2-3 except that aluminum oxide (Al 2 O 3 ) is used as an additive in the preparation process of lithium manganese oxide, so that the molar percentage of Al and Mn in lithium manganese oxide is 0.42%, the rest are the same as in Example 1- 2 is the same.
  • Al 2 O 3 aluminum oxide
  • Example 2-4 except that titanium dioxide (TiO 2 ) is used as an additive in the preparation process of the lithium manganese oxide, so that the molar percentage of Ti and Mn in the lithium manganese oxide is 0.42%, the rest is the same as that of Example 1-2.
  • TiO 2 titanium dioxide
  • Example 2-5 except that the molar percentage of Nb and Mn in the lithium manganese oxide is 0.014% in the preparation process of the lithium manganese oxide, the rest is the same as that of Example 1-2.
  • Example 2-6 except that the molar percentage of Nb and Mn in the lithium manganese oxide is 0.70% in the preparation process of the lithium manganese oxide, the rest is the same as that of Example 1-2.
  • Example 2-7 except that the molar percentage of Nb and Mn in the lithium manganese oxide is 1.39% in the preparation process of the lithium manganese oxide, the rest is the same as that of Example 1-2.
  • Example 2-8 except that the mole percentage of Nb and Mn in the lithium manganese oxide is 1.74% in the preparation process of the lithium manganese oxide, the rest is the same as that of Example 1-2.
  • Example 3-1 to Example 3-5 except that (Dv90 ⁇ Dv10)/Dv50 was adjusted according to Table 3, the rest was the same as that of Example 1-2.
  • Example 4-1 to Example 4-3 except that the compacted density of the positive electrode sheet is adjusted according to Table 3, the rest is the same as that of Example 1-2.
  • Example 4-4 to Example 4-5 except that the compacted density of the negative electrode sheet is adjusted according to Table 3, the rest is the same as that of Example 1-2.
  • Example 6-1 to Example 6-4 in addition to adding the compound 1,3-propane sultone containing sulfur and oxygen double bonds in ⁇ Preparation of Electrolyte>, and based on the quality of the electrolyte, adjust according to Table 5 Except for the mass percentage of the compound containing sulfur-oxygen double bonds, the rest are the same as in Example 1-2.
  • Comparative Example 1-1 except that in the preparation process of lithium manganese oxide, the ratio of raw materials lithium carbonate and manganese dioxide is 0.540:1, the rest is the same as that of Example 1-1.
  • the performance parameters of embodiment 1-1 to embodiment 1-8, comparative example 1-1 are as shown in table 1, the performance parameters of embodiment 2-1 to embodiment 2-8 are as shown in table 2, embodiment 3- 1 to embodiment 3-5, the performance parameter of embodiment 4-1 to embodiment 4-5 is as shown in table 3, the performance parameter of embodiment 5-1 to embodiment 5-2 is as shown in table 4, embodiment The performance parameters of 6-1 to embodiment 6-4 are as shown in table 5:
  • Examples 1-1 to 1-8 have better high-temperature storage performance and high-temperature cycle performance, especially high-temperature cycle performance, compared to Comparative Example 1-1 in which the lattice parameter a of lithium manganese oxide is not within the range It has been significantly improved, and is not limited to any theory.
  • the possible reason is that: when the SOC of the lithium-ion battery is 15%, the lattice parameter a of the lithium manganese oxide is regulated within the above range, then under this SOC, the lithium manganese oxide The amount of lithium delithiation is relatively moderate, and the change of its own crystal structure is relatively small, which can inhibit the storage and attenuation of lithium manganese oxides at a lower SOC, which is beneficial to the lithium manganese oxides in the lithium-ion battery cycle (that is, 0% SOC to 100% SOC) to maintain a stable crystal structure, thereby improving the high-temperature cycle performance of the electrochemical device.
  • the types of doping elements in lithium manganese oxide and the mole percentages of doping elements M and Mn usually also affect the high-temperature storage performance and high-temperature cycle performance of the electrochemical device. From Example 1-2, Example 2-1 to Example 2-8, it can be seen that compared with the undoped design of Example 2-1, doping Nb, Mg, Al, and Ti elements can improve the positive electrode.
  • the density of active material particles reduces the ratio of Mn 3+ /Mn 4+ , improves structural stability, improves the amount of Mn deposited on the negative electrode, and significantly improves the high-temperature storage and high-temperature cycle performance of the battery. Comparing Example 1-2, Example 2-5 to Example 2-8, with the increase of doping amount, the improvement of high temperature performance is more significant, while the low temperature performance is slightly reduced.
  • Example 3-1 to Example 3-5 it can be seen that within a certain range, with the increase of (Dv90-Dv10)/Dv50, the particle distribution range is wider, which is more conducive to the matching of large and small particles , under the same compaction density, the pressure and crushing degree of the particles are reduced, which is beneficial to reduce the Mn dissolution of the positive electrode, improve the Mn deposition amount of the negative electrode and the uniformity of Mn distribution of the negative electrode sheet, and obtain better high-temperature storage performance and high-temperature cycle performance .
  • both too wide and too narrow particle distribution will bring adverse effects.
  • the low (Dv99-Dv10)/Dv50 will lead to unreasonable particle size matching.
  • Example 4-1 to Example 4-5 it can be seen that within a certain range, with the increase in the compaction density of the positive electrode sheet, the contact between the material particles is better, which is conducive to Improve the conductive network, but it will increase particle breakage, thereby increasing Mn dissolution and reducing the stability of the material surface, resulting in reduced high-temperature storage and high-temperature cycle performance.
  • the increase of the compaction density of the negative electrode sheet it may lead to the deposition and uneven distribution of Mn on the negative electrode, causing side reactions such as lithium analysis in some areas, affecting the battery interface, and thus reducing the cycle life.
  • the potential of the negative electrode sheet to Li usually also affects the high-temperature storage performance and high-temperature cycle performance of the electrochemical device. From Example 1-2, Example 5-1 to Example 5-2, it can be seen that Example 1-2 and Example 5-2 in which the potential of the negative pole piece to Li is ⁇ 0.56V have more excellent High-temperature cycle performance. This is because the potential of the negative electrode gradually increases during the discharge process. When the lithium-ion battery is fully discharged at 0% SOC, the potential of the negative electrode is the highest. SEI is unstable at a higher potential and prone to decomposition and gas production, thereby reducing High temperature cycle performance.
  • Example 6-1 to Example 6-4 when based on the quality of the electrolyte, the content of the compound 1,3-propane sultone containing sulfur and oxygen double bonds is between 0.01% and When the concentration is 1.00%, the high-temperature storage performance and high-temperature cycle performance of the lithium-ion battery can be further improved, thereby further balancing the comprehensive performance of the lithium-ion battery.
  • the content of 1,3-propane sultone in the electrolyte is too high (Example 6-4), the high-temperature storage and cycle performance will not be significantly improved, but the low-temperature performance will be reduced instead.

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Abstract

一种电化学装置及包含电化学装置的电子装置，电化学装置包括负极极片和正极极片，负极极片包括负极活性材料层，负极活性材料层包括负极活性材料，正极极片包括正极活性材料层，正极活性材料层包括正极活性材料，正极活性材料包括锂锰氧化合物；电化学装置的SOC＝15％时，锂锰氧化物的晶格参数 ɑ≤8.2008Å。电化学装置具有良好的高温存储性能和循环性能。

Description

电化学装置及包含该电化学装置的电子装置 技术领域
本申请涉及电化学领域，具体涉及一种电化学装置及包含该电化学装置的电子装置。
背景技术
锂离子电池由于具有储能密度大、开路电压高、自放电率低、循环寿命长、安全性能好等优点，广泛应用于电能储存、移动电子设备、电动自行车、电动汽车和航天航空设备等各个领域。
锂离子电池的性能主要取决于正极极片、负极极片、隔离膜和电解液的特性。通常，正极极片中的正极活性材料是影响锂离子电池性能的重要因素之一。其中，锰酸锂作为常用的正极活性材料，广泛应用于电动自行车及电动汽车领域。但是，单独使用锰酸锂存在高温存储性能差，使用寿命短的问题。
发明内容
本申请的目的在于提供一种电化学装置及包含该电化学装置的电子装置，以改善电化学装置的高温存储性能和高温循环性能。
本申请的第一方面提供了一种电化学装置，其包括正极极片和负极极片，所述负极极片包括负极活性材料层，所述负极活性材料层包括负极活性材料，正极极片包括正极活性材料层，正极活性材料层包括正极活性材料，正极活性材料包括锂锰氧化物；电化学装置的SOC(荷电状态)＝15％时，锂锰氧化物的晶格参数
Figure PCTCN2021126833-appb-000001
例如，锂锰氧化物的晶格参数a为
Figure PCTCN2021126833-appb-000002
Figure PCTCN2021126833-appb-000003
或上述任两个数值范围间的任一数值。不限于任何理论，电化学装置的SOC＝15％时，锂锰氧化物的晶格参数a调控在上述范围内，能够使锂锰氧化物在电化学装置整个SOC变化范围内(即0％SOC至100％SOC范围)均能够维持稳定的晶体结构，从而改善电化学装置的高温循环性能。同时，还能够减少电化学装置充放电循环过程中锂锰氧化物的结构畸变、抑制Mn(锰)离子的溶出，使负极Mn的分布更加均匀，减少对负极上SEI(固体电解质界面)膜的破坏，从而改善电化学装置的高温存储性能。此外，还可以改善负极析锂，提高电化学装置的安全性能。
在本申请的一些实施方案中，锂锰氧化物包括Li xMn 2-yM yO 4，其中，0.9≤x≤1.1，0 ≤y≤0.05，M包括Al、Mg、Ti、Cr、Cu、Fe、Co、W、Zn、Ga、Zr、Ru、Ag、Sn、Au、La、Ce、Pr、Nd、Sm、Nb或Gd中的至少一种。
在本申请的一些实施方案中，正极活性材料还包括锂过渡金属复合氧化物或锂过渡金属磷酸化合物中的至少一种。
在本申请的一些实施方案中，所述锂过渡金属复合氧化物包括Li x1Ni y1Co z1Mn kZ qO 2± aT a，其中，Z包括B、Mg、Al、Si、P、S、Ti、Cr、Fe、Cu、Zn、Ga、Y、Zr、Mo、Ag、W、In、Sn、Pb、Sb或Ce中的至少一种，T为卤素；其中，0.2<x1≤1.2、0≤y1≤1、0≤z1≤1、0≤k≤1、0≤q≤1，且y1、z1、k不同时为0，以及0≤a≤1；
在本申请的一些实施方案中，所述锂过渡金属磷酸化合物包括Li x2R y2N z2PO 4，其中，R包括Fe或Mn中的至少一种；N包括Al、Ti、V、Cr、Co、Li、Ni、Cu、Zn、Mg、Ga、Zr、Nb或Si中的至少一种；其中，0.6≤x2≤1.2，0.95≤y2≤1，0≤z2≤0.05。
在本申请的一些实施方案中，基于正极活性材料的质量，正极活性材料中Mn的质量百分含量W1为42％至47％。例如，基于正极活性材料的质量，Mn的质量百分含量为42％、42.3％、46.9％、47％或上述任两个数值范围间的任一数值。不限于任何理论，正极活性材料中Mn的质量百分含量W1调控在上述范围内，正极活性材料中的锰酸锂的比例适当，能够降低锰酸锂材料本身高温存储性能较差的影响，保证其它活性材料对Mn溶出的改善效果，抑制Mn的溶出和其在负极的沉积，从而提升电化学装置的高温循环性能；同时，能够进一步提升电化学装置的低温放电性能。
在本申请的一些实施方案中，基于负极活性材料的质量，负极活性材料中Mn的质量百分含量W2小于或等于0.1％。例如，基于负极活性材料的质量，Mn的质量百分含量为0.0050％、0.0100％、0.0150％、0.0201％、0.0230％、0.0265％、0.0280％、0.0294％、0.0300％、0.0320％、0.0340％、0.0350％、0.0450％、0.0550％、0.0650％、0.0750％、0.0850％、0.0950％、0.1％或上述任两个数值范围间的任一数值。不限于任何理论，负极活性材料中Mn的质量百分含量W2小于或等于0.1％，能够降低破坏负极SEI膜的稳定性的风险，进而提升电化学装置的高温存储性能。
在本申请的一些实施方案中，负极极片包括第一区域、第二区域、以及位于第一区域和第二区域之间的第三区域，基于第一区域中负极活性材料的质量，第一区域中Mn的质量百分含量V1；基于第二区域中负极活性材料的质量，第二区域中Mn的质量百分含量 V2；基于第三区域中负极活性材料的质量，第三区域中Mn的质量百分含量V3；V1、V2和V3中的最大值与最小值之间的差值为ΔV，V1、V2和V3的平均值为V，满足：ΔV/V≤20％。例如，ΔV/V的值可以为0％、1.45％、3％、4％、5％、7.8％、9.2％、10.4％、10.5％、10.8％、11％、11.5％、11.8％、11.9％、12.1％、12.3％、12.4％、12.5％、13％、17％、19％、20％或上述任两个数值范围间的任一数值。不限于任何理论，ΔV/V值调控在上述范围内，能够降低负极极片中Mn分布的差异性，Mn分布均匀能够使负极表面动力学和稳定性差异较小，降低负极副反应和析锂风险，提升电化学装置的高温使用寿命和安全可靠性。其中，第一区域包括负极极片在宽度方向上的第一侧边至距第一侧边的距离为10mm的区域，第一侧边上设置有极耳；第二区域包括负极极片在宽度方向上的第二侧边至距第二侧边的距离为10mm的区域，第二侧边与第一侧边相对。
在本申请中，对第一区域中Mn的质量百分含量V1、第二区域中Mn的质量百分含量V2、第三区域中Mn的质量百分含量V3没有特别限制，只要能够实现本申请目的即可。例如，第一区域中Mn的质量百分含量V1为0.1020％至0.1100％。第二区域中Mn的质量百分含量V2为0.0950％至0.1000％。第三区域中Mn的质量百分含量V3为0.1020％至0.1100％。
在本申请的一些实施方案中，锂锰氧化物包括掺杂元素M，掺杂元素M包括Nb、Al、Mg、Ti、Cr、Mo、Zr、Y或B中的至少一种，锂锰氧化物中的掺杂元素M与Mn的摩尔百分比为0.01％至2％。例如，锂锰氧化物中的掺杂元素M与Mn的摩尔百分比为0.014％、0.42％、0.70％、1.39％、1.74％或上述任两个数值范围间的任一数值。不限于任何理论，锂锰氧化物中的掺杂元素M与Mn的摩尔百分比过大(例如大于2％)，电化学装置的高温循环性能和高温存储性能可能不再显著提升，且会存在降低电化学装置容量的风险；锂锰氧化物中的掺杂元素M与Mn的摩尔百分比过小(例如小于0.01％)，对电化学装置高温循环性能和高温存储性能的改善效果可能不明显。将锂锰氧化物中的掺杂元素M与Mn的摩尔百分比调控在上述范围内，锂锰氧化物的颗粒致密度提高，锂锰氧化物中Mn 3+/Mn 4+的比例降低，锂锰氧化物的结构稳定性提高，能够有效改善负极Mn的沉积量，从而提高电化学装置的高温存储性能和高温循环性能。
在本申请的一些实施方案中，正极活性材料的颗粒粒径分布满足：1.2≤(Dv90－Dv10)/Dv50≤2.2。例如，(Dv90－Dv10)/Dv50的值为1.2、1.32、1.48、2.2或上述任两个数值范围间的任一数值。不限于任何理论，将(Dv90－Dv10)/Dv50的值调控在上述范围内，正极活性材料的颗粒分布范围更宽，更有利于大粒径颗粒和小粒径颗粒的合理搭配，在相 同的压实密度下，正极材料颗粒受到的压力和破碎程度减小，更有利于减少正极的Mn溶出，改善负极Mn沉积量和负极极片Mn分布的均匀性，从而使电化学装置的高温存储性能和高温循环性能得以进一步提升。
本申请对正极活性材料的Dv10、Dv50和Dv90没有特别限制，只要能够实现本申请目的即可。例如，正极活性材料的Dv10为0.9μm至6μm。正极活性材料的Dv50为9μm至18μm。正极活性材料的Dv90为19μm至35μm。
在本申请中，Dv10表示颗粒在体积基准的粒度分布中，从小粒径侧起，达到体积累积10％的粒径。Dv50表示颗粒在体积基准的粒度分布中，从小粒径侧起，达到体积累积50％的粒径。Dv90表示颗粒在体积基准的粒度分布中，从小粒径侧起，达到体积累积90％的粒径。
在本申请的一些实施方案中，电化学装置的SOC＝0％时，负极极片对Li的电位小于0.6V。由于负极极片对Li的电位在电化学装置的放电过程中逐渐升高，电化学装置的SOC＝0％时，负极极片对Li的电位最高，SEI膜在较高的电位下不稳定，容易发生分解产气，增加负极表面的稳定性降低的风险。因此，电化学装置的SOC＝0％时，负极极片对Li的电位小于0.6V，电化学装置的负极界面在高温下的副反应减少，电化学装置的高温循环性能和使用寿命得到提升。
在本申请的一些实施方案中，正极活性材料层的压实密度为2.8g/cm 3至3.05g/cm 3。例如，正极活性材料层的压实密度为2.8g/cm 3、2.95g/cm 3、3.05g/cm 3或上述任两个数值范围间的任一数值。不限于任何理论，正极活性材料层的压实密度调控在上述范围内，正极活性材料颗粒破碎的风险降低，能够抑制Mn溶出、提升正极活性材料层的界面稳定性；同时，正极活性材料颗粒间的接触更好，有利于改善导电网络的导电性，更好的调控Mn的溶出和正极活性材料层的界面稳定性，从而更有利于改善电化学装置的高温存储性能和高温循环性能。
在本申请的一些实施方案中，负极活性材料层的压实密度为1.45g/cm 3至1.65g/cm 3。例如，负极活性材料层的压实密度为1.45g/cm 3、1.55g/cm 3、1.65g/cm 3或上述任两个数值范围间的任一数值。不限于任何理论，负极活性材料层的压实密度调控在上述范围内，负极活性材料颗粒破碎的风险降低，同时，更有利于调控正极溶出的Mn在负极的沉积量和分布的均匀性，从而更有利于改善电化学装置的高温存储性能和高温循环性能。
在本申请的一些实施方案中，正极活性材料层的孔隙率α为15％至40％。例如，孔隙率α为15％、20％、25％、30％、35％、40％或上述任两个数值范围间的任一数值。不限于任何理论，孔隙率α调控在上述范围内，能够抑制电化学装置在充放电循环过程中出现正极活性材料颗粒间的接触失效，导致电化学装置的循环性能和能量密度降低；同时，能够保证正极活性材料被电解液充分浸润，减小锂离子的传输距离，提升电化学装置的动力学性能。
在本申请中，正极活性材料层的孔隙率α是指，正极活性材料层中各组分间孔隙的体积与正极活性材料层表观体积的百分比。
在本申请的一些实施方案中，电化学装置的SOC＝100％时，正极极片的DSC(差示扫描量热法)曲线上的放热峰的起始位置在260℃至280℃之间。表明电化学装置具有良好的热稳定性，从而具有良好的高温存储性能、高温循环性能和安全性能。
在本申请的一些实施方案中，电化学装置还包括电解液，电解液包括含有硫氧双键的化合物；基于电解液的质量，含有硫氧双键的化合物的质量百分含量为0.01％至1.00％。例如，含有硫氧双键的化合物的质量百分含量为0.01％、0.50％、1.00％或上述任两个数值范围间的任一数值。不限于任何理论，通过将含有硫氧双键的化合物的质量百分含量调控在上述范围内，更有利于进一步改善电化学装置的高温存储性能和高温循环性能，由此进一步平衡电化学装置的综合性能。
本申请对含有硫氧双键的化合物的种类没有特别限制，只要能够实现本申请目的即可。例如，含有硫氧双键的化合物可以包括1,3-丙烷磺内酯或硫酸乙烯酯中的至少一种。
本申请的电解液还包括锂盐和非水溶剂。本申请对锂盐的种类没有特别限制，只要能够实现本申请目的即可。例如，锂盐可以包含六氟磷酸锂(LiPF 6)、LiCH 3SO 3、LiCF 3SO 3、LiN(SO 2CF 3) 2、LiC(SO 2CF 3) 3或LiSiF 6中的至少一种。优选地，可以包含LiPF 6，因为LiPF 6可以给出高的离子电导率，并改善锂离子电池的高温循环性能。本申请对非水溶剂没有特别限制，只要能够实现本申请目的即可。例如，非水溶剂可以包含碳酸酯化合物、羧酸酯化合物、醚化合物或其它有机溶剂中的至少一种。上述碳酸酯化合物可为链状碳酸酯化合物或环状碳酸酯化合物中的至少一种。上述链状碳酸酯化合物可以包括碳酸二甲酯(DMC)、碳酸二乙酯(DEC)、碳酸二丙酯(DPC)、碳酸甲丙酯(MPC)、碳酸乙丙酯(EPC)或碳酸甲乙酯(MEC)中的至少一种。环状碳酸酯化合物可以包括碳酸乙烯酯(EC)、碳酸丙烯酯(PC)或碳酸亚丁酯(BC)中的至少一种。上述羧酸酯化合物可以包括乙酸乙酯、 乙酸正丙酯、乙酸叔丁酯、丙酸甲酯、丙酸乙酯或丙酸丙酯中的至少一种。上述醚化合物可以包括二丁醚、四甘醇二甲醚、二甘醇二甲醚、1,2-二甲氧基乙烷、1,2-二乙氧基乙烷、乙氧基甲氧基乙烷、2-甲基四氢呋喃或四氢呋喃中的至少一种。上述其它有机溶剂可以包括二甲亚砜、1,2-二氧戊环、环丁砜、甲基环丁砜、1,3-二甲基-2-咪唑烷酮、N-甲基-2-吡咯烷酮、甲酰胺、二甲基甲酰胺、乙腈、磷酸三甲酯、磷酸三乙酯、磷酸三辛酯或磷酸酯中的至少一种。
本申请对负极活性材料的种类没有特别限制，只要能够实现本申请目的即可。例如，负极活性材料可以包括天然石墨、人造石墨、中间相微碳球(MCMB)、硬碳、软碳、硅、硅-碳复合物、SiO x(0<x<2)、Li-Sn合金、Li-Sn-O合金、Sn、SnO、SnO 2、尖晶石结构的钛酸锂Li 4Ti 5O 12、Li-Al合金或金属锂中的至少一种。
本申请的负极极片还包括负极集流体。本申请对负极集流体没有特别限制，只要能够实现本申请目的即可。例如，负极集流体可以包含铜箔、铜合金箔、镍箔、不锈钢箔、钛箔、泡沫镍、泡沫铜或复合集流体等。在本申请中，对负极集流体和负极活性材料层的厚度没有特别限制，只要能够实现本申请目的即可。例如，负极集流体的厚度为6μm至10μm，单面负极活性材料层的厚度为30μm至130μm。在本申请中，负极活性材料层可以设置于负极集流体厚度方向上的一个表面上，也可以设置于负极集流体厚度方向上的两个表面上。需要说明，这里的“表面”可以是负极集流体的全部区域，也可以是负极集流体的部分区域，本申请没有特别限制，只要能实现本申请目的即可。任选地，负极极片还可以包含导电层，导电层位于负极集流体和负极活性材料层之间。本申请对导电层的组成没有特别限制，可以是本领域常用的导电层。例如，导电层包括导电剂和粘结剂。
本申请的正极极片还包括正极集流体。本申请对正极集流体没有特别限制，只要能够实现本申请目的即可。例如，正极集流体可以包含铝箔、铝合金箔或复合集流体等。在本申请中，对正极集流体和正极活性材料层的厚度没有特别限制，只要能够实现本申请目的即可。例如，正极集流体的厚度为5μm至20μm，优选为6μm至18μm。单面正极活性材料层的厚度为30μm至120μm。在本申请中，正极活性材料层可以设置于正极集流体厚度方向上的一个表面上，也可以设置于正极集流体厚度方向上的两个表面上。需要说明，这里的“表面”可以是正极集流体的全部区域，也可以是正极集流体的部分区域，本申请没有特别限制，只要能实现本申请目的即可。任选地，正极极片还可以包含导电层，导电层位于正极集流体和正极活性材料层之间。本申请对导电层的组成没有特别限制，可以是本领域常用的导电层。例如，导电层包括导电剂和粘结剂。
本申请对上述导电剂和粘结剂没有特别限制，只要能够实现本申请目的即可。例如，导电剂可以包括导电炭黑(Super P)、碳纳米管(CNTs)、碳纳米纤维、鳞片石墨、乙炔黑、炭黑、科琴黑、碳点、碳纳米管或石墨烯中的至少一种。例如，粘结剂可以包括聚丙烯醇、聚丙烯酸钠、聚丙烯酸钾、聚丙烯酸锂、聚酰亚胺、聚酰亚胺、聚酰胺酰亚胺、丁苯橡胶(SBR)、聚乙烯醇(PVA)、聚偏氟乙烯、聚偏二氟乙烯(PVDF)、聚四氟乙烯(PTFE)、聚乙烯醇缩丁醛(PVB)、水性丙烯酸树脂、羧甲基纤维素(CMC)或羧甲基纤维素钠(CMC-Na)中的至少一种。
本申请的电化学装置还包括隔膜，用以分隔正极极片和负极极片，防止锂离子电池内部短路，允许电解质离子自由通过，完成电化学充放电过程的作用。本申请中的隔膜没有特别限制，只要能够实现本申请目的即可。例如，聚乙烯(PE)、聚丙烯(PP)为主的聚烯烃(PO)类隔膜，聚酯膜(例如聚对苯二甲酸二乙酯(PET)膜)、纤维素膜、聚酰亚胺膜(PI)、聚酰胺膜(PA)、氨纶、芳纶膜、织造膜、非织造膜(无纺布)、微孔膜、复合膜、隔膜纸、碾压膜或纺丝膜中的至少一种。例如，隔膜可以包括基材层和表面处理层。基材层可以为具有多孔结构的无纺布、膜或复合膜，基材层的材料可以包括聚乙烯、聚丙烯、聚对苯二甲酸乙二醇酯或聚酰亚胺中的至少一种。任选地，可以使用聚丙烯多孔膜、聚乙烯多孔膜、聚丙烯无纺布、聚乙烯无纺布或聚丙烯-聚乙烯-聚丙烯多孔复合膜。任选地，基材层的至少一个表面上设置有表面处理层，表面处理层可以是聚合物层或无机物层，也可以是混合聚合物与无机物所形成的层。例如，无机物层包括无机颗粒和粘结剂，所述无机颗粒没有特别限制，例如可以选自氧化铝、氧化硅、氧化镁、氧化钛、二氧化铪、氧化锡、二氧化铈、氧化镍、氧化锌、氧化钙、氧化锆、氧化钇、碳化硅、勃姆石、氢氧化铝、氢氧化镁、氢氧化钙或硫酸钡中的至少一种。所述粘结剂没有特别限制，例如可以选自聚偏氟乙烯、偏氟乙烯-六氟丙烯的共聚物、聚酰胺、聚丙烯腈、聚丙烯酸酯、聚丙烯酸、聚丙烯酸盐、聚乙烯呲咯烷酮、聚乙烯醚、聚甲基丙烯酸甲酯、聚四氟乙烯或聚六氟丙烯中的至少一种。聚合物层中包含聚合物，聚合物的材料包括聚酰胺、聚丙烯腈、丙烯酸酯聚合物、聚丙烯酸、聚丙烯酸盐、聚乙烯呲咯烷酮、聚乙烯醚、聚偏氟乙烯或聚(偏氟乙烯-六氟丙烯)中的至少一种。
本申请的电化学装置没有特别限制，其可以包括发生电化学反应的任何装置。在一些实施例中，电化学装置可以包括但不限于：锂金属二次电池、锂离子二次电池、锂聚合物二次电池或锂离子聚合物二次电池等。
电化学装置的制备过程为本领域技术人员所熟知的，本申请没有特别的限制，例如， 可以包括但不限于以下步骤：将正极极片、隔膜和负极极片按顺序堆叠，并根据需要将其卷绕、折叠等操作得到卷绕结构的电极组件，将电极组件放入包装壳内，将电解液注入包装壳并封口，得到电化学装置；或者，将正极极片、隔膜和负极极片按顺序堆叠，然后用胶带将整个叠片结构的四个角固定好得到叠片结构的电极组件，将电极组件置入包装壳内，将电解液注入包装壳并封口，得到电化学装置。此外，也可以根据需要将防过电流元件、导板等置于包装壳中，从而防止电化学装置内部的压力上升、过充放电。
本申请的第二方面提供了一种电子装置，包含本申请前述任一方案所述的电化学装置。该电子装置具有良好的高温存储性能和高温循环性能。
本申请的电子装置没有特别限制，其可以包括但不限于以下种类：笔记本电脑、笔输入型计算机、移动电脑、电子书播放器、便携式电话、便携式传真机、便携式复印机、便携式打印机、头戴式立体声耳机、录像机、液晶电视、手提式清洁器、便携CD机、迷你光盘、收发机、电子记事本、计算器、存储卡、便携式录音机、收音机、备用电源、电机、汽车、摩托车、助力自行车、自行车、照明器具、玩具、游戏机、钟表、电动工具、闪光灯、照相机、家庭用大型蓄电池和锂离子电容器等。
本申请提供了一种电化学装置及包含该电化学装置的电子装置，该电化学装置包括负极极片和正极极片，负极极片包括负极活性材料层，负极活性材料层包括负极活性材料，正极极片包括正极活性材料层，正极活性材料层包括正极活性材料，正极活性材料包括锂锰氧化合物；电化学装置的SOC＝15％时，锂锰氧化物的晶格参数
Figure PCTCN2021126833-appb-000004
通过在电化学装置处于15％SOC状态下，将正极活性材料中的锂锰氧化物的晶格参数a调控在≤
Figure PCTCN2021126833-appb-000005
范围内，使锂锰氧化物在合适的SOC下仍能维持较为稳定的晶体结构，从而改善电化学装置的高温循环性能，同时，锂锰氧化物的晶体结构在充放电循环期间更加稳定，Mn离子的溶出得到有效抑制，还能有效提高电化学装置的高温存储性能。
具体实施方式
为使本申请的目的、技术方案、及优点更加清楚明白，以下参照实施例，对本申请进一步详细说明。显然，所描述的实施例仅仅是本申请一部分实施例，而不是全部的实施例。基于本申请中的实施例，本领域普通技术人员所获得的所有其他技术方案，都属于本申请保护的范围。
需要说明的是，本申请的具体实施方式中，以锂离子电池作为电化学装置的例子来解 释本申请，但是本申请的电化学装置并不仅限于锂离子电池。
实施例
以下，举出实施例及对比例来对本申请的实施方式进行更具体地说明。各种的试验及评价按照下述的方法进行。另外，只要无特别说明，“％”为质量基准。
测试方法和设备：
锂锰氧化物的晶格参数a的测试：
将锂离子电池在25℃的环境中静置30min，然后以0.2C倍率恒流充电至4.2V，以4.2V恒压充电至0.05C，静置30min，接着以0.5C倍率放电至2.8V，记录此时的放电容量为锂离子电池的实际容量；然后按照实际容量以0.1C恒流充电9min，调整锂离子电池的SOC＝15％；拆解锂离子电池得到正极极片，并将其浸泡在DMC(碳酸二甲酯)溶液中24小时，干燥备用；使用XRD(X射线衍射仪)对所制备的极片进行测试并精修得到锂锰氧化物的晶格参数a。
正极活性材料中各元素含量的测试：
将锂离子电池满放至2.8V，拆解正极极片，并将其浸泡在DMC溶液中24h，干燥后从正极极片上刮下正极活性材料层，火焰灼烧去除粘结剂和导电剂后得到正极活性材料粉末备用。将处理后的正极活性材料粉末取6个平行样，分别称重、消解、稀释，然后使用Thermo ICAP6300型号的电感耦合等离子体发射光谱仪测试不同元素的质量百分含量，求平均值，其中，各元素的质量百分含量为正极活性材料中的质量百分含量。
负极活性材料中Mn含量测试：
将锂离子电池满放至2.8V，拆解得到负极极片，并将其浸泡在DMC溶液中24h，干燥备用；沿极片宽度方向将极片分为三个区域，第一区域为靠近极耳侧边缘至极片中心方向10mm的区域，第二区域为非极耳侧边缘至极片中心方向10mm的区域，第三区域为极片中剩余部分；在处理后的负极极片的第一区域、第二区域和第三区域分别取6个平行样，分别称重、消解、稀释，然后使用Thermo ICAP6300型号的电感耦合等离子体发射光谱仪测试Mn元素的质量百分含量，并求平均值，所测得第一区域、第二区域、第三区域中Mn的质量百分含量均值分别为V1、V2、V3。定义负极Mn含量V为V1、V2、V3的均值，V1、V2、V3中的最大值与最小值之间的差值为ΔV。
正极活性材料的Dv10、Dv50和Dv90的测试：
使用激光粒度仪测试正极活性材料的Dv10、Dv50和Dv90。
负极极片对Li的电位测试：
将锂离子电池满放至2.8V，使用多路数据记录仪测试满放状态下负极极片对Li的电位。
正极活性材料层的压实密度的测试：
正极活性材料层的压实密度Pc通过公式：Pc＝mc/Vc计算得出。式中，mc为正极活性材料层的质量，单位：g；Vc为正极活性材料层的体积，单位：cm 3，其中，体积Vc是正极活性材料层的面积Sc与正极活性材料层的厚度之积。
负极活性材料层的压实密度的测试：
负极活性材料层的压实密度Pa通过公式：Pa＝ma/Va计算得出。式中，ma为负极活性材料层的质量，单位：g；Va为负极活性材料层的体积，单位：cm 3，其中，体积Va是负极活性材料层的面积Sa与负极活性材料层的厚度之积。
正极活性材料层孔隙率α的测试：
冲切半径为d的正极极片，使用万分尺测量正极极片的厚度h1，并装入AccuPyc 1340仪器的样品仓中，在密闭的样品仓中采用氦气(He)对极片进行填充，由此利用波尔定律PV＝nRT测得正极极片的真体积V。测试完成后，清洗去正极极片表面的正极活性材料层，使用万分尺测量集流体的厚度为h2，计算出正极活性材料层的表观体积πd 2×(h1-h2)。最后通过如下公式获得正极活性材料层的孔隙率α＝1-(V-πd 2×h2)/[πd 2×(h1-h2)]。
DSC的测试：
DSC用来测量试样和参比物的热流差和温度的关系。采用STA449F3型号同步热分析仪测试DSC曲线，方法如下：调整锂离子电池SOC＝100％，拆解锂离子电池，取出正极极片，利用DMC清洗后，裁切成10cm×10cm的规格，测试温度范围150℃至400℃，升温速率10℃/min，得到DSC曲线。
高温循环性能的测试：
在45℃的环境中，将锂离子电池在0.5C的充电电流下进行恒流，直到上限电压为4.2V， 然后在1C的放电电流下进行恒流放电，直到最终电压为2.8V，记录首次循环的放电容量。然后以相同的步骤进行500次的充电和放电循环，记录第500次循环锂离子电池的放电容量。
锂离子电池的循环容量保持率(％)＝(第500次循环的放电容量/首次循环的放电容量)×100％。
每个实施例或对比例测试4个样品，取平均值。
高温存储性能的测试：
将锂离子电池在25℃的环境中静置30min，然后以0.2C倍率恒流充电至4.2V，以4.2V恒压充电至0.05C，静置30min，接着以0.5C倍率放电至2.8V，记录此时的放电容量为锂离子电池的实际容量，为存储前容量；然后将满充状态的电池置于60℃烘箱存储7天后，按相同步骤测试其可逆容量，为存储后容量。
锂离子电池的高温存储容量保持率(％)＝存储后容量/存储前容量×100％。
低温性能的测试：
将锂离子电池在25℃的环境中静置30min，然后以0.2C倍率恒流充电至4.2V，以4.2V恒压充电至0.05C，静置30min，接着以0.5C倍率放电至2.8V，记录此时的放电容量为锂离子电池25℃的实际容量C1；然后将锂离子电池在-10℃的环境中静置60min后再以0.2C倍率恒流充电至4.2V，以4.2V恒压充电至0.05C，静置30min，接着以0.5C倍率放电至2.8V，记录此时的放电容量为锂离子电池-10℃的实际容量C2。通过下式计算-10℃放电容量保持率：放电容量保持率＝C2/C1×100％。
实施例1-1
<正极活性材料的制备>
将原料碳酸锂和二氧化锰按照Li:Mn摩尔比为0.545:1进行混合，加入一定量的五氧化二铌(Nb 2O 5)作为添加剂，使锂锰氧化物中Nb与Mn的摩尔百分比为0.42％，反应生成锂锰氧化物。
将上述锂锰氧化物和层状镍钴锰酸锂Li(Ni 0.55Co 0.15Mn 0.30)O 2按照质量比80:20混合，得到正极活性材料。
<正极极片的制备>
将制备得到的正极活性材料、导电剂乙炔黑、粘结剂聚偏二氟乙烯(PVDF)按照重量比96.5:2:1.5进行混合，加入NMP(N-甲基吡咯烷酮)作为溶剂，调配成为固含量为75％的浆料，并在真空搅拌机作用下搅拌至体系成均匀的正极浆料。将正极浆料均匀涂覆在厚度为10μm的正极集流体铝箔的一个表面上，90℃条件下烘干，得到涂层厚度为110μm的单面涂布正极活性材料层的正极极片。之后，在该正极极片的另一个表面上重复以上步骤，即得到双面涂布正极活性材料层的正极极片。90℃条件下烘干后以2.95g/cm 3的压实密度冷压后，再经裁片、焊接极耳，得到正极极片。
<负极极片的制备>
将负极活性材料人造石墨、导电剂乙炔黑、粘结剂SBR、增稠剂羧甲基纤维素钠按照质量比95:2:2:1进行混合，然后加入去离子水调配成为固含量为70％的负极浆料，并在真空搅拌机作用下搅拌至体系成均匀的负极浆料。将负极浆料均匀涂覆在厚度为8μm的负极集流体铜箔的一个表面上，90℃条件下烘干，得到涂层厚度为130μm的单面涂布负极活性材料层的负极极片。之后，在该负极的另一个表面上重复以上步骤，即得到双面涂布负极活性材料层的负极极片。90℃条件下烘干后以1.55g/cm 3的压实密度冷压后，再经裁片、焊接极耳，得到负极极片。
<隔膜的制备>
采用厚度为14μm的PE多孔聚合物薄膜。
<电解液的制备>
在含水量小于10ppm的氩气气氛手套箱中，将碳酸丙烯酯(PC)、碳酸乙烯酯(EC)、碳酸二乙酯(DEC)按质量比1:1:1均匀混合，得到有机溶剂。加入锂盐LiPF 6并混合均匀，得到基础电解液。其中，LiPF 6的质量浓度为12.5％。
<锂离子电池的制备>
将上述制备的正极极片、隔膜、负极极片按顺序叠好，使隔膜处于正极极片和负极极片中间起到隔离的作用，然后卷绕得到电极组件。将电极组件装入铝塑膜包装壳中，放置在85℃真空烘箱中干燥12h脱去水分，注入上述配好的电解液，经过真空封装、静置、化成、脱气、整形等工序得到锂离子电池。
实施例1-2中，除了在锂锰氧化物的制备过程中，原料碳酸锂和二氧化锰的Li:Mn摩尔比为0.560：1，其余与实施例1-1相同。
实施例1-3中，除了锂锰氧化物、磷酸铁锂LiFePO 4和层状镍钴锰酸锂Li(Ni 0.55Co 0.15Mn 0.30)O 2按照质量比80:15:5混合作为正极活性材料，其余与实施例1-2相同。
实施例1-4中，除了锂锰氧化物、磷酸铁锂LiFePO 4和层状镍钴锰酸锂Li(Ni 0.55Co 0.15Mn 0.30)O 2按照质量比80:10:10混合作为正极活性材料，其余与实施例1-3相同。
实施例1-5中，除了在锂锰氧化物的制备过程中，原料碳酸锂和二氧化锰的Li:Mn摩尔比为0.575：1，其余与实施例1-4相同。
实施例1-6中，除了在锂锰氧化物的制备过程中，原料碳酸锂和二氧化锰的Li:Mn摩尔比为0.575：1，其余与实施例1-1相同。
实施例1-7中，除了在锂锰氧化物的制备过程中，原料碳酸锂和二氧化锰的Li:Mn摩尔比为0.580：1，其余与实施例1-1相同。
实施例1-8中，除了在锂锰氧化物的制备过程中，原料碳酸锂和二氧化锰的Li:Mn摩尔比为0.580：1，其余与实施例1-5相同。
实施例2-1中，除了在锂锰氧化物的制备过程中无添加剂五氧化二铌，其余与实施例1-2相同。
实施例2-2中，除了在锂锰氧化物的制备过程中添加剂使用氧化镁(MgO)、使锂锰氧化物中Mg与Mn的摩尔百分比为0.42％，其余与实施例1-2相同。
实施例2-3中，除了在锂锰氧化物的制备过程中添加剂使用氧化铝(Al 2O 3)、使锂锰氧化物中Al与Mn的摩尔百分比为0.42％，其余与实施例1-2相同。
实施例2-4中，除了在锂锰氧化物的制备过程中添加剂使用二氧化钛(TiO 2)、使锂锰氧化物中Ti与Mn的摩尔百分比为0.42％，其余与实施例1-2相同。
实施例2-5中，除了在锂锰氧化物的制备过程中使锂锰氧化物中Nb与Mn的摩尔百分比为0.014％，其余与实施例1-2相同。
实施例2-6中，除了在锂锰氧化物的制备过程中使锂锰氧化物中Nb与Mn的摩尔百分比为0.70％，其余与实施例1-2相同。
实施例2-7中，除了在锂锰氧化物的制备过程中使锂锰氧化物中Nb与Mn的摩尔百分比为1.39％，其余与实施例1-2相同。
实施例2-8中，除了在锂锰氧化物的制备过程中使锂锰氧化物中Nb与Mn的摩尔百分比为1.74％，其余与实施例1-2相同。
实施例3-1至实施例3-5中，除了按照表3调整(Dv90－Dv10)/Dv50以外，其余与实施例1-2相同。
实施例4-1至实施例4-3中，除了按照表3调整正极极片的压实密度以外，其余与实施例1-2相同。
实施例4-4至实施例4-5中，除了按照表3调整负极极片的压实密度以外，其余与实施例1-2相同。
实施例5-1至实施例5-2中，除了通过匹配正极极片和负极极片的首次效率调整所制备的锂离子电池荷电状态为0％SOC状态时，负极极片对Li的电位以外，其余与实施例1-2相同。
实施例6-1至实施例6-4中，除了在<电解液的制备>中加入含有硫氧双键的化合物1,3-丙烷磺内酯，并基于电解液的质量，按照表5调整含有硫氧双键的化合物的质量百分含量以外，其余与实施例1-2相同。
对比例1-1中，除了在锂锰氧化物的制备过程中，原料碳酸锂和二氧化锰的比例为0.540：1，其余与实施例1-1相同。
实施例1-1至实施例1-8、对比例1-1的性能参数如表1所示，实施例2-1至实施例2-8的性能参数如表2所示，实施例3-1至实施例3-5、实施例4-1至实施例4-5的性能参数如表3所示，实施例5-1至实施例5-2的性能参数如表4所示，实施例6-1至实施例6-4的性能参数如表5所示：
表1
Figure PCTCN2021126833-appb-000006
从实施例1-1至实施例1-8和对比例1-1中可以看出，锂离子电池的高温存储性能和高温循环性能随着SOC＝15％时，锂锰氧化物晶格参数a的变化而变化。锂离子电池的SOC＝15％时，锂锰氧化物的晶格参数
Figure PCTCN2021126833-appb-000007
的实施例1-1至实施例1-8具有更好的高温存储性能和高温循环性能，特别是高温循环性能，相对于锂锰氧化物的晶格参数a不在范围内的对比例1-1得到了显著提升，不限于任何理论，可能的原因在于：锂离子电池的SOC＝15％时，锂锰氧化物的晶格参数a调控在上述范围内，则在该SOC下，锂锰氧化物的脱锂量较为适中，自身晶体结构的变化相对较小，能够抑制锂锰氧化物在较低SOC下存储衰减过快，有利于锂锰氧化物在锂离子电池循环过程中(即0％SOC至100％SOC变化范围内)维持稳定的晶体结构，从而改善电化学装置的高温循环性能。同时，还能够减少锂离子电池充放电循环过程中锂锰氧化物的结构畸变、抑制Mn(锰)离子的溶出，使负极Mn的分布更加均匀，减少对负极上SEI(固体电解质界面)膜的破坏，从而改善锂离子电池的高温存储性能。
表2
Figure PCTCN2021126833-appb-000008
锂锰氧化物中掺杂元素的种类以及掺杂元素M与Mn的摩尔百分比通常也会对电化学装置的高温存储性能和高温循环性能产生影响。从实施例1-2、实施例2-1至实施例2-8中可以看出，相比实施例2-1无掺杂的设计方案，掺杂Nb,Mg,Al,Ti元素能够提高正极活性材料颗粒的致密度，降低Mn 3+/Mn 4+比例，提高结构稳定性，改善负极Mn的沉积量，对电池的高温存储和高温循环性能改善显著。对比实施例1-2、实施例2-5至实施例2-8，随掺杂量增加，高温性能的改善更加显著，同时低温性能略有降低。
表3
Figure PCTCN2021126833-appb-000009
Figure PCTCN2021126833-appb-000010
从实施例1-2、实施例3-1至实施例3-5中可以看出，在一定范围内随(Dv90-Dv10)/Dv50增加，颗粒分布范围更宽，更有利于大小颗粒的搭配，在相同压实密度下颗粒所受到的压力和破碎程度减少，有利于减少正极的Mn溶出，改善负极Mn沉积量和负极极片Mn分布均匀性，获得更好的高温存储性能和高温循环性能。但过宽和过窄的颗粒分布都会带来不利的影响，如实施例3-4，(Dv99-Dv10)/Dv50偏低会导致大小颗粒搭配的不合理，在极片冷压过程中部分颗粒间会存在较多的间隙，或者部分颗粒存在过压而破裂，从而增加Mn溶出，使高温性能下降，如实施例3-5，(Dv99-Dv10)/Dv50偏高，同样会导致大小颗粒搭配的不合理，降低高温存储和循环性能。
从实施例1-2、实施例4-1至实施例4-5中可以看出，在一定的范围内，随正极极片压实密度的增加，材料颗粒之间的接触更好，有利于改善导电网络，但会增加颗粒破碎，从而增加Mn溶出和降低材料表面的稳定性，导致高温存储和高温循环性能降低。另外，随负极极片压实密度的增加，可能会导致Mn在负极的沉积和分布不均，引起部分区域析锂等副反应，影响电池界面，从而使循环寿命下降。
表4
Figure PCTCN2021126833-appb-000011
Figure PCTCN2021126833-appb-000012
负极极片对Li的电位通常也会对电化学装置的高温存储性能和高温循环性能产生影响。从实施例1-2、实施例5-1至实施例5-2中可以看出，负极极片对Li的电位≤0.56V的实施例1-2和实施例5-2，具有更加优异的高温循环性能，这是由于负极电位在放电过程中逐渐升高，锂离子电池在0％SOC的满放状态时负极电位最高，SEI在较高的电位下不稳定容易发生分解产气，从而降低高温循环性能。
表5
Figure PCTCN2021126833-appb-000013
从实施例1-2、实施例6-1至实施例6-4可以看出，当基于电解液的质量，含有硫氧双键的化合物1,3-丙烷磺内酯的含量在0.01％到1.00％时，可进一步改善锂离子电池的高温存储性能和高温循环性能，由此进一步平衡锂离子电池的综合性能。当电解液中1,3-丙烷磺内酯含量过高时(实施例6-4)对高温存储及循环性能没有进一步明显的改善，反而会降低低温性能。
以上所述仅为本申请的较佳实施例，并不用以限制本申请，凡在本申请的精神和原则之内，所做的任何修改、等同替换、改进等，均应包含在本申请保护的范围之内。

Claims (13)

  1. 一种电化学装置，其包括正极极片和负极极片，所述负极极片包括负极活性材料层，所述负极活性材料层包括负极活性材料，所述正极极片包括正极活性材料层，所述正极活性材料层包括正极活性材料，所述正极活性材料包括锂锰氧化物；
    所述电化学装置的SOC＝15％时，所述锂锰氧化物的晶格参数
    Figure PCTCN2021126833-appb-100001
  2. 根据权利要求1所述的电化学装置，其中，所述电化学装置满足以下特征中的至少一者：
    (a)基于所述正极活性材料的质量，所述正极活性材料中的Mn的质量百分含量W1为42％至47％；
    (b)基于所述负极活性材料的质量，所述负极活性材料中的Mn的质量百分含量W2小于或等于0.1％；
    (c)所述负极极片包括第一区域、第二区域、以及位于所述第一区域和第二区域之间的第三区域，基于所述第一区域中负极活性材料的质量，所述第一区域中的Mn的质量百分含量V1；基于所述第二区域中负极活性材料的质量，所述第二区域中的Mn的质量百分含量V2；基于所述第三区域中负极活性材料的质量，所述第三区域中的Mn的质量百分含量V3；所述V1、V2和V3中的最大值与最小值之间的差值为ΔV，所述V1、V2和V3的平均值为V，满足：ΔV/V≤20％；
    第一区域包括所述负极极片在宽度方向上的第一侧边至距所述第一侧边的距离为10mm的区域，所述第一侧边上设置有极耳；
    所述第二区域包括所述负极极片在宽度方向上的第二侧边至距所述第二侧边的距离为10mm的区域，所述第二侧边与所述第一侧边相对。
  3. 根据权利要求1所述的电化学装置，其中，所述锂锰氧化物包括掺杂元素M，所述掺杂元素M包括Nb、Al、Mg、Ti、Cr、Mo、Zr、Y或B中的至少一种，所述锂锰氧化物中的掺杂元素M与Mn的摩尔百分比为0.01％至2％。
  4. 根据权利要求1所述的电化学装置，其中，所述正极活性材料的颗粒粒径分布满足：1.2≤(Dv90－Dv10)/Dv50≤2.2。
  5. 根据权利要求1所述的电化学装置，其中，所述电化学装置的SOC＝0％时，所述负 极极片对Li的电位小于0.6V。
  6. 根据权利要求1所述的电化学装置，其中，所述电化学装置满足以下特征中的至少一者：
    (d)所述正极活性材料层的压实密度为2.8g/cm 3至3.05g/cm 3；
    (e)所述负极活性材料层的压实密度为1.45g/cm 3至1.65g/cm 3。
  7. 根据权利要求1所述的电化学装置，其中，所述正极极片的孔隙率α为15％至40％。
  8. 根据权利要求1所述的电化学装置，其中，所述电化学装置的SOC＝100％时，所述正极极片的DSC曲线上的放热峰的起始位置在260℃至280℃之间。
  9. 根据权利要求1所述的电化学装置，其中，所述电化学装置还包括电解液，所述电解液包括含有硫氧双键的化合物。
  10. 根据权利要求9所述的电化学装置，其中，基于所述电解液的质量，所述含有硫氧双键的化合物的质量百分含量为0.01％至1.00％。
  11. 根据权利要求1所述的电化学装置，其中，所述电化学装置满足以下特征中的至少一者：
    (f)所述锂锰氧化物包括Li xMn 2-yM yO 4，其中，0.9≤x≤1.1，0≤y≤0.05，M包括Al、Mg、Ti、Cr、Cu、Fe、Co、W、Zn、Ga、Zr、Ru、Ag、Sn、Au、La、Ce、Pr、Nd、Sm、Nb或Gd中的至少一种；
    (g)所述正极活性材料还包括锂过渡金属复合氧化物或锂过渡金属磷酸化合物中的至少一种。
  12. 根据权利要求11所述的电化学装置，其中，所述电化学装置满足以下特征中的至少一者：
    (h)所述锂过渡金属复合氧化物包括Li x1Ni y1Co z1Mn kZ qO 2±aT a，其中，Z包括B、Mg、Al、Si、P、S、Ti、Cr、Fe、Cu、Zn、Ga、Y、Zr、Mo、Ag、W、In、Sn、Pb、Sb或Ce中的至少一种，T为卤素；其中，0.2<x1≤1.2、0≤y1≤1、0≤z1≤1、0≤k≤1、0≤q≤1，且y1、z1、k不同时为0，以及0≤a≤1；
    (i)所述锂过渡金属磷酸化合物包括Li x2R y2N z2PO 4，其中，R包括Fe或Mn中的至 少一种；N包括Al、Ti、V、Cr、Co、Li、Ni、Cu、Zn、Mg、Ga、Zr、Nb、Si中的至少一种；其中，0.6≤x2≤1.2，0.95≤y2≤1，0≤z2≤0.05。
  13. 一种电子装置，其包括权利要求1至12中任一项所述的电化学装置。
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