WO2025066565A1 - 半固态锂电池及包含其的终端 - Google Patents

半固态锂电池及包含其的终端 Download PDF

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Publication number
WO2025066565A1
WO2025066565A1 PCT/CN2024/110298 CN2024110298W WO2025066565A1 WO 2025066565 A1 WO2025066565 A1 WO 2025066565A1 CN 2024110298 W CN2024110298 W CN 2024110298W WO 2025066565 A1 WO2025066565 A1 WO 2025066565A1
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positive electrode
coating
negative electrode
oxide electrolyte
semi
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French (fr)
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WO2025066565A9 (zh
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李文文
吴霞
崔厚磊
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Honor Device Co Ltd
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Honor Device Co Ltd
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Publication of WO2025066565A9 publication Critical patent/WO2025066565A9/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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • 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
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
    • H01M10/0562—Solid materials
    • 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
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • H01M10/0585—Construction or manufacture of accumulators having only flat construction elements, i.e. flat positive electrodes, flat negative electrodes and flat separators
    • 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
    • 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
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/665—Composites
    • H01M4/667—Composites in the form of layers, e.g. coatings
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
    • H01M50/417—Polyolefins
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/431—Inorganic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
    • H01M50/451—Separators, membranes or diaphragms characterised by the material having a layered structure comprising layers of only organic material and layers containing inorganic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
    • H01M50/457—Separators, membranes or diaphragms characterised by the material having a layered structure comprising three or more layers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/46—Separators, membranes or diaphragms characterised by their combination with electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2220/00—Batteries for particular applications
    • H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2220/00—Batteries for particular applications
    • H01M2220/30—Batteries in portable systems, e.g. mobile phone, laptop
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0068—Solid electrolytes inorganic
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0068—Solid electrolytes inorganic
    • H01M2300/0071—Oxides
    • 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 battery technology, and in particular to a semi-solid lithium battery and a terminal comprising the same.
  • the impedance of lithium-ion batteries is composed of ohmic internal resistance, SEI film interface impedance, charge transfer impedance, ion diffusion internal resistance, etc. As the battery energy density increases, the battery's interface impedance gradually increases, and the battery's low-temperature performance and high-temperature performance decrease accordingly, resulting in a shortened battery life of mobile electronic devices.
  • the present application provides a semi-solid lithium battery and a terminal comprising the same.
  • the semi-solid lithium battery provided in the present application has good high-temperature performance, low-temperature performance and high-rate discharge capacity, and can extend the battery life of terminals such as mobile electronic devices at high or low temperatures.
  • the present application provides a semi-solid lithium battery, comprising:
  • a positive electrode sheet and a negative electrode sheet are respectively arranged on both sides of the diaphragm;
  • the positive electrode plate comprises a positive electrode current collector and a positive electrode active layer disposed on the positive electrode current collector; the positive electrode active layer is doped with 0.1 wt% to 5 wt% of an oxide electrolyte, and the D50 of the oxide electrolyte is 0.05 ⁇ m to 1.2 ⁇ m;
  • the negative electrode plate includes a negative electrode current collector and a negative electrode active layer disposed on the negative electrode current collector.
  • an oxide electrolyte with a D50 of 0.05 ⁇ m to 1.2 ⁇ m is added to the positive electrode material at a doping amount of 0.1 wt% to 5 wt% to form a positive electrode active layer, which can reduce the minimum liquid retention coefficient of the battery from 1.55 g/Ah to below 1.41 g/Ah; reduce the expansion rate of high-temperature cycles of 1000 cls from 15% to below 13.1%; increase the capacity retention rate of the battery at high temperature cycles of 1000 cls from 58% to more than 70%; increase the capacity retention rate at -20°C from about 50% to more than 55%; increase the number of -20°C loading times from 20 times to more than 50 times; increase the 2C/0.2C rate discharge capacity, but the degree of improvement is not obvious; increase the hot box temperature from 126°C to more than 130°C.
  • the experimental results show that too small or too large a particle size of the oxide electrolyte has no significant improvement on the above properties, and may even deteriorate the above properties,
  • the present application adds an oxide electrolyte with a D50 of 0.05 ⁇ m to 1.2 ⁇ m to the negative electrode material at a doping amount of 0.1 wt% to 5 wt% to form a negative electrode active layer, that is, both the positive electrode active layer and the negative electrode active layer are doped with an oxide electrolyte, which can further reduce the minimum liquid retention coefficient of the battery to below 1.35 g/Ah; reduce the expansion of the high temperature cycle 1000 cls rate, to below 12.2%; increase the capacity retention rate of the battery at high temperature cycle of 1000cls, to more than 70%; increase the capacity retention rate at -20°C, to more than 60%; increase the number of -20°C loading times, to more than 60 times; increase the 2C/0.2C rate discharge capacity, to more than 94%; increase the hot box temperature to more than 132°C.
  • too small or too large particle size of oxide electrolyte has no obvious effect on further improvement of the above performance, but will affect the performance improvement brought by doping oxide
  • the present application provides a coating including an oxide electrolyte on at least one side of the diaphragm, preferably on both sides, which can further reduce the minimum liquid retention coefficient of the battery to below 1.30g/Ah; reduce the expansion rate of high-temperature cycling for 1000cls to below 11.5%; increase the capacity retention rate of the battery after 1000cls of high-temperature cycling to more than 77%; increase the capacity retention rate at -20°C to more than 65%; increase the number of loading times at -20°C to more than 90 times; increase the 2C/0.2C rate discharge capacity to more than 95%; and increase the hot box temperature to above 134°C.
  • the present application provides a coating including an oxide electrolyte between the positive electrode collector and the positive electrode active layer and/or between the negative electrode collector and the negative electrode active layer to further improve the safety performance of the battery, especially the puncture safety and extrusion safety.
  • This application introduces an oxidizing electrolyte with a D50 of 0.05 ⁇ m to 1.2 ⁇ m into the positive electrode active layer and the negative electrode active layer, and further forms a coating containing an oxidizing electrolyte on the separator and the current collector, thereby reducing the ion transfer impedance at the electrode/electrolyte interface, so that the positive and negative electrodes have an interface with faster ion transfer, while improving the electrode/electrolyte interface stability, thereby significantly improving the low temperature performance, rate discharge performance, high temperature performance and safety of the battery.
  • the lithium-ion battery provided in this application can be used in consumer products, such as terminals, including mobile phones, watches, tablets and other devices; it can also be used in power products, such as automobiles, etc., which can significantly improve the product's performance at low and high temperatures and extend its endurance.
  • FIG1 is a schematic structural diagram of a semi-solid lithium battery provided in a first embodiment of the present application.
  • FIG2 is a schematic diagram of the structure of a semi-solid lithium battery provided in a second embodiment of the present application.
  • FIG3 is a schematic structural diagram of a semi-solid lithium battery provided in a third embodiment of the present application.
  • FIG4 is a diagram showing the -20°C capacity retention rate of the batteries provided in Comparative Example 1 and Example 5;
  • FIG. 5 is a SOC-RSS curve of the batteries provided in Comparative Example 1 and Example 5.
  • the words “exemplary” or “for example” are used to indicate examples, illustrations or descriptions. Any embodiment or design described as “exemplary” or “for example” in the application embodiments should not be interpreted as being more preferred or more advantageous than other embodiments or designs. Specifically, the use of words such as “exemplary” or “for example” is intended to present related concepts in a specific way.
  • the present invention discloses a semi-solid lithium battery, comprising:
  • a positive electrode sheet and a negative electrode sheet are respectively arranged on both sides of the diaphragm;
  • the positive electrode plate comprises a positive electrode current collector and a positive electrode active layer disposed on the positive electrode current collector; the positive electrode active layer is doped with 0.1 wt% to 5 wt% of an oxide electrolyte, and the D50 of the oxide electrolyte is 0.05 ⁇ m to 1.2 ⁇ m;
  • the negative electrode plate includes a negative electrode current collector and a negative electrode active layer disposed on the negative electrode current collector.
  • FIG. 1 is a schematic diagram of the structure of a semi-solid lithium battery provided in the first embodiment of the present application, wherein 11 is an electrolyte, 12 is a separator, 13 is a positive electrode collector, 14 is a positive electrode active layer, 15 is a negative electrode collector, and 16 is a negative electrode active layer.
  • the semi-solid lithium battery provided in the present application includes an electrolyte 11, which is a non-aqueous solvent electrolyte, including a non-aqueous solvent, a lithium salt and an optional additive.
  • the non-aqueous solvent includes a cyclic carbonate and a chain carbonate.
  • the cyclic carbonate includes but is not limited to one or more of ethylene carbonate (EC) or propylene carbonate (PC)
  • the chain carbonate includes but is not limited to one or more of dimethyl carbonate (DMC), diethyl carbonate (DEC) and ethyl methyl carbonate (EMC).
  • the non-aqueous solvent includes ethylene carbonate, propylene carbonate and diethyl carbonate, and the mass ratio of ethylene carbonate, propylene carbonate and diethyl carbonate is preferably 1 to 5:1 to 5:1 to 5, more preferably 3:3:4.
  • the lithium salt is an electrolyte, including but not limited to one or more of lithium hexafluorophosphate, lithium difluorooxalatoborate, lithium difluorophosphate (LiPO 2 F 2 ) and lithium difluorosulfonyl imide (LiFSI), preferably lithium hexafluorophosphate.
  • the concentration of the lithium salt in the electrolyte is preferably 10 wt% to 20 wt%, more preferably 12.5 wt% to 16 wt%.
  • the present application has no special restrictions on the type and amount of the additive, which can be selected according to the battery function, and the present application will not elaborate on this.
  • the semi-solid lithium battery provided in the present application includes a diaphragm 12 disposed in an electrolyte 11, and the diaphragm 12 is used to separate the positive electrode plate from the negative electrode plate.
  • the present application has no special restrictions on the material and thickness of the diaphragm, and any diaphragm commonly used in the art can be used, such as a 9 ⁇ m thick PE diaphragm.
  • the positive electrode plate is arranged on one side of the diaphragm 12, and the negative electrode plate is arranged on the side of the diaphragm 12.
  • the positive electrode sheet includes a positive electrode current collector 13 and a positive electrode active layer 14 disposed on the positive electrode current collector.
  • the present application has no special limitation on the positive electrode current collector 13, and any positive electrode current collector well known to those skilled in the art can be used, such as an aluminum foil with a thickness of 8 ⁇ m.
  • the present application doped 0.1wt% to 5wt% of oxide electrolyte with D50 of 0.05 ⁇ m to 1.2 ⁇ m in the positive electrode active layer, which can reduce the minimum liquid retention coefficient of the battery, reduce the expansion rate of high-temperature cycle 1000cls, improve the capacity retention rate of the battery high-temperature cycle 1000cls, improve the capacity retention rate at -20°C, increase the number of -20°C loading, increase the 2C/0.2C rate discharge capacity, and increase the hot box temperature.
  • the experimental results show that the oxide electrolyte particle size is too small, such as less than 10nm, or too large, such as greater than 1.5 ⁇ m, which has no obvious improvement effect on the above performance, and may even deteriorate the above performance, especially the number of low-temperature loading.
  • the positive electrode active layer includes a positive electrode active material, a conductive agent, a binder and an oxide electrolyte, wherein the positive electrode active material includes but is not limited to one or more of a ternary positive electrode material, lithium cobalt oxide, manganese-rich lithium, nickel manganese spinel, lithium iron phosphate, lithium iron manganese phosphate, and lithium manganese oxide; wherein the chemical formula of the ternary positive electrode material can be LiNi x Co y Mn 1-xy O2, 0.7 ⁇ x ⁇ 1, 0 ⁇ y ⁇ 0.3.
  • Conductive agents include, but are not limited to, one or more of conductive carbon black, acetylene black, Ketjen black, conductive graphite, conductive carbon fiber, carbon nanotubes, metal powder, and carbon fiber; binders include, but are not limited to, one or more of styrene butadiene rubber (SBR), carboxymethyl cellulose (CMC), polyvinylidene fluoride (PVDF), polymethyl methacrylate (PMMA), polyacrylonitrile (PAN), and polyethylene oxide (PEO).
  • SBR styrene butadiene rubber
  • CMC carboxymethyl cellulose
  • PVDF polyvinylidene fluoride
  • PMMA polymethyl methacrylate
  • PAN polyacrylonitrile
  • PEO polyethylene oxide
  • the mass ratio of the positive electrode active material, the conductive agent, and the binder is 70-99: 0.5-15: 0.5-15, preferably 75-99: 1-10: 1-10, and more preferably 80-99: 1-5: 1-5.
  • the positive electrode active layer is doped with 0.1 wt% to 5 wt% of an oxide electrolyte, that is, the oxide electrolyte accounts for 0.1 wt% to 5 wt% of the total amount of the positive electrode active material, the conductive agent and the binder, preferably 0.2 wt% to 4 wt%, more preferably 0.5 wt% to 3 wt%.
  • the D50 of the oxide electrolyte is 0.05 ⁇ m to 1.2 ⁇ m, preferably 0.08 ⁇ m to 1 ⁇ m, more preferably 0.1 ⁇ m to 1 ⁇ m.
  • the oxide electrolyte may be selected from one or more of NASICON structure materials, perovskite structure materials, antiperovskite structure materials, LISICON structure materials and garnet structure materials, including but not limited to Li 1.4 Al 0.4 Ti 1.6 (PO4) 3 , Li 1.5 Al 0.5 Ge 1.5 (PO4) 3 , Li 7 La 3 Zr 2 O 12 , Li 6.4 La 3 Zr 2 Ta 0.6 O 12 and La 0.56 Li 0.33 TiO 3 , etc., preferably Li 1.4 Al 0.4 Ti 1.6 (PO4) 3 or Li 7 La 3 Zr 2 O 12 .
  • the negative electrode plate includes a negative electrode current collector 15 and a negative electrode active layer 16 disposed on the negative electrode current collector 15.
  • the present application has no special limitation on the negative electrode current collector 15, and any negative electrode current collector well known to those skilled in the art can be used, such as a copper foil with a thickness of 8 ⁇ m.
  • the negative electrode active layer includes a negative electrode active material, a conductive agent and a binder, wherein the negative electrode active material includes but is not limited to one or more of carbon materials, silicon-based materials, metallic lithium or lithium alloys, preferably one or two of graphite or silicon-based materials; the conductive agent includes but is not limited to one or more of conductive carbon black, acetylene black, Ketjen black, conductive graphite, conductive carbon fiber, carbon nanotubes, metal powder, and carbon fiber; the binder includes but is not limited to one or more of styrene butadiene rubber (SBR), carboxymethyl cellulose (CMC), polyvinylidene fluoride (PVDF), polymethyl methacrylate (PMMA), polyacrylonitrile (PAN), and polyethylene oxide (PEO).
  • the mass ratio of the negative electrode active material, the conductive agent and the binder is 70-99:0.5-15:0.5-15, preferably 75-99:1-10:1
  • the present application dopes 0.1wt% to 5wt% of an oxide electrolyte with a D50 of 0.05 ⁇ m to 1.2 ⁇ m in the negative electrode active layer to further reduce the minimum liquid retention coefficient of the battery, reduce the expansion rate of 1000cls of high-temperature cycles, increase the capacity retention rate of 1000cls of high-temperature cycles of the battery, increase the capacity retention rate at -20°C, increase the number of -20°C loading, increase the 2C/0.2C rate discharge capacity, and increase the hot box temperature.
  • the experimental results show that the oxide electrolyte particle size is too small, such as less than 10nm, or too large, such as greater than 1.5 ⁇ m, which has no obvious improvement effect on the above performance, and may even deteriorate the above performance, especially the number of low-temperature loading.
  • the negative electrode active layer is doped with 0.1 wt% to 5 wt% of an oxide electrolyte, that is, the oxide electrolyte accounts for 0.1 wt% to 5 wt% of the total amount of the negative electrode active material, the conductive agent and the binder, preferably 0.2 wt% to 4 wt%, more preferably 0.5 wt% to 3 wt%.
  • the D50 of the oxide electrolyte is 0.05 ⁇ m to 1.2 ⁇ m, preferably 0.08 ⁇ m to 1 ⁇ m, more preferably 0.1 ⁇ m to 1 ⁇ m.
  • the oxide electrolyte may be selected from one or more of NASICON structure materials, perovskite structure materials, antiperovskite structure materials, LISICON structure materials and garnet structure materials, including but not limited to Li 1.4 Al 0.4 Ti 1.6 (PO4) 3 , Li 1.5 Al 0.5 Ge 1.5 (PO4) 3 , Li 7 La 3 Zr 2 O 12 , Li 6.4 La 3 Zr 2 Ta 0.6 O 12 and La 0.56 Li 0.33 TiO 3 , etc., preferably Li 1.4 Al 0.4 Ti 1.6 (PO4) 3 or Li 7 La 3 Zr 2 O 12 .
  • At least one side of the diaphragm is provided with a coating including an oxide electrolyte
  • a coating including an oxide electrolyte referring to FIG2 , which is a schematic structural diagram of a semi-solid lithium battery provided in the second embodiment of the present application, wherein 21 is an electrolyte, 22 is a diaphragm, 23 is a positive electrode current collector, 24 is a positive electrode active layer, 25 is a negative electrode current collector, 26 is a negative electrode active layer, 221 is a first coating, and 222 is a second coating.
  • the present application provides a coating containing a solid oxide on at least one side of the diaphragm, which can further reduce the minimum liquid retention coefficient of the battery to below 1.30g/Ah; reduce the expansion rate of the high-temperature cycle of 1000cls to below 11.5%; increase the capacity retention rate of the battery after 1000cls of high-temperature cycle to more than 77%; increase the capacity retention rate at -20°C to more than 65%; increase the number of -20°C loading times to more than 90 times; increase the 2C/0.2C rate discharge capacity to more than 95%; and increase the hot box temperature to above 134°C.
  • the electrolyte 21, the separator 22, the positive electrode current collector 23, the positive electrode active layer 24, the negative electrode current collector 25 and the negative electrode active layer 26 are as described above, and the present application will not repeat them here.
  • the first coating 221 includes an oxide electrolyte and a binder, and the mass ratio of the solid oxide electrolyte to the binder is preferably 0.05-0.5:5-15, more preferably 0.1-0.2:8-12.
  • the thickness of the first coating 221 is preferably 0.5 ⁇ m-5 ⁇ m, more preferably 1 ⁇ m-2 ⁇ m.
  • the oxide electrolyte and the binder are as described above, and this application will not repeat them here.
  • the second coating 222 is similar to the first coating 221, which may be the same or different, and this application will not repeat them here.
  • FIG3 is a schematic diagram of the structure of a semi-solid lithium battery provided in the third embodiment of the present application, wherein 31 is an electrolyte, 32 is a separator, 33 is a positive electrode current collector, 34 is a positive electrode active layer, 35 is a negative electrode current collector, 36 is a negative electrode active layer, 321 is a first coating, 322 is a second coating, 331 is a third coating, and 351 is a fourth coating.
  • the electrolyte 31, the separator 32, the positive electrode current collector 33, the positive electrode active layer 34, the negative electrode current collector 35, the negative electrode active layer 36, the first coating 321, and the second coating 322 are as described above, and the present application will not repeat them here.
  • the third coating 331 includes an oxide electrolyte and a binder, and the mass ratio of the solid oxide electrolyte to the binder is preferably 0.05-0.5:5-15, more preferably 0.1-0.2:8-12.
  • the thickness of the third coating 331 is preferably 0.5 ⁇ m-5 ⁇ m, more preferably 1 ⁇ m-2 ⁇ m.
  • the oxide electrolyte and binder are as described above, and this application will not be repeated here.
  • the fourth coating 351 is similar to the third coating 331, which may be the same or different, and this application will not be repeated here.
  • the present invention provides a fifth coating layer including an oxide electrolyte on the side of the positive electrode current collector away from the positive electrode active layer, and/or provides a sixth coating layer including an oxide electrolyte on the side of the negative electrode current collector away from the negative electrode active layer.
  • the fifth coating layer and the sixth coating layer are similar to the first coating layer, and are not described in detail in this application.
  • the positive electrode active layer is doped with 0.15 wt% to 3.5 wt% of an oxide electrolyte, and the D50 of the oxide electrolyte is 0.05 ⁇ m to 1 ⁇ m; the oxide electrolyte is selected from Li 1.4 Al 0.4 Ti 1.6 (PO 4 ) 3 or Li 7 La 3 Zr 2 O 12 .
  • the negative electrode active layer is doped with 0.15 wt% to 3.5 wt% of an oxide electrolyte, and the D50 of the oxide electrolyte is 0.05 ⁇ m to 1 ⁇ m; the oxide electrolyte is selected from Li 1.4 Al 0.4 Ti 1.6 (PO 4 ) 3 .
  • the D50 of the oxide electrolyte is independently 0.05 ⁇ m to 1.2 ⁇ m; and the oxide electrolyte is independently selected from Li 1.4 Al 0.4 Ti 1.6 (PO 4 ) 3 or Li 7 La 3 Zr 2 O 12 .
  • the D50 of the oxide electrolyte is independently 0.05 ⁇ m to 1.2 ⁇ m; and the oxide electrolyte is independently selected from Li 1.4 Al 0.4 Ti 1.6 (PO 4 ) 3 or Li 7 La 3 Zr 2 O 12 .
  • the D50 of the oxide electrolyte is independently 0.05 ⁇ m to 1.2 ⁇ m; and the oxide electrolyte is independently selected from Li 1.4 Al 0.4 Ti 1.6 (PO 4 ) 3 or Li 7 La 3 Zr 2 O 12 .
  • the semi-solid lithium battery provided in the present application has the following performance parameters: the minimum liquid retention coefficient is 1.25-1.45g/Ah; the capacity retention rate of high-temperature cycle 1000cls is more than 65%; the expansion rate of high-temperature cycle 1000cls is less than 14%; the capacity retention rate at -20°C is more than 55%; the number of -20°C loading times is more than 45 times; the 2C/0.2C rate discharge capacity is more than 92%; and the hot box temperature is above 130°C.
  • the present invention also provides a method for preparing the above-mentioned semi-solid lithium battery, comprising the following steps:
  • a positive electrode active layer on a positive electrode collector with a positive electrode slurry comprising a positive electrode active material, a conductive agent, a binder and an oxide electrolyte to obtain a positive electrode sheet
  • a negative electrode active layer on a negative electrode collector with a negative electrode slurry comprising a negative electrode active material, a conductive agent and a binder to obtain a negative electrode sheet
  • Assemble a semi-solid lithium battery by combining a positive electrode sheet, a negative electrode sheet, a separator and an electrolyte.
  • the positive electrode slurry can be prepared according to the following method:
  • the positive electrode active material, the conductive agent, the binder, the oxide electrolyte and the solvent are mixed to obtain a positive electrode slurry.
  • the positive electrode slurry can be prepared according to the following method:
  • the composite, a binder, a conductive agent and a solvent are mixed to obtain a positive electrode slurry.
  • the pre-sintering temperature is no greater than 400° C., preferably 200-400° C.
  • the oxide electrolyte and the positive electrode active material are pre-sintered to make the oxide electrolyte and the positive electrode active material more uniformly mixed, thereby further improving the performance of the battery.
  • the positive electrode slurry is coated on the positive electrode current collector, and the positive electrode sheet is obtained after drying, cold pressing, cutting, slitting and drying.
  • the negative electrode slurry also includes an oxide electrolyte
  • the preparation method of the negative electrode plate is similar to the preparation method of the positive electrode plate, which will not be described in detail in this application.
  • a coating containing an oxide electrolyte is formed on at least one side, preferably both sides, of the separator, and the preparation method thereof is as follows:
  • the slurry containing oxide electrolyte and binder is coated on the surface of the diaphragm, and then dried and cold pressed to form a coating.
  • the present application has no particular limitation on the coating method, and coating can be performed by spraying, gravure printing, and the like.
  • a step of forming a coating layer containing an oxide electrolyte on the positive electrode collector or the negative electrode collector is also included.
  • the coating layer may be formed on the side of the positive electrode collector facing the positive electrode active layer or on the side of the negative electrode collector facing the negative electrode active layer, or may be formed on both sides of the positive electrode collector or the negative electrode collector. The method for forming the coating layer is as described above, and this application will not be repeated here.
  • the semi-solid lithium-ion battery provided in this application can be used in consumer products, such as terminals, including mobile phones, watches, tablets and other devices; it can also be used in power products, such as automobiles, etc., to improve the product's performance and battery life at low or high temperatures.
  • the present application also provides a terminal, including the semi-solid lithium battery described in the above technical solution.
  • the terminal mentioned in the present application can be any device with communication and storage functions, such as smart phones, cellular phones, cordless phones, Session Initiation Protocol (SIP) phones, tablet computers, personal digital assistants (PADs), laptop computers, digital cameras, e-book readers, portable multimedia players, handheld devices with wireless communication functions, computing devices or other processing devices connected to wireless modems, vehicle-mounted devices, wearable devices, 5G terminal devices, etc., and the embodiments of the present application are not limited to this.
  • the lithium ion battery and the preparation method thereof provided by the present application are described in detail below in conjunction with the embodiments.
  • ethylene carbonate (EC), propylene carbonate (PC) and diethyl carbonate (DEC) are mixed uniformly in a mass ratio of 3:3:4 to obtain a non-aqueous solvent, and then fully dried lithium salt LiPF6 is dissolved in the non-aqueous solvent to make the mass percentage of LiPF6 in the electrolyte be 12.5%, and mixed uniformly to obtain an electrolyte.
  • a Cu foil with a thickness of 8 ⁇ m was used as the negative electrode current collector, and an Al foil with a thickness of 8 ⁇ m was used as the positive electrode current collector.
  • the negative electrode active material artificial graphite/Si composite material, the binder styrene-butadiene rubber (SBR), and the thickener sodium carboxymethyl cellulose (CMC) are mixed in a weight ratio of 97.4:1.2:1.4, and fully stirred and mixed in an appropriate amount of deionized water to form a uniform negative electrode slurry; the slurry is coated on the negative electrode collector, dried, and cold pressed to obtain a negative electrode sheet.
  • Lithium cobalt oxide (LiCoO 2 ), conductive carbon black (Super P) and polyvinylidene fluoride were added to the solid electrolyte according to the formula shown in Table 1 in a mass ratio of 97:1.4:1.6, and N-methylpyrrolidone (NMP) was added and stirred evenly using a vacuum mixer to obtain a positive electrode slurry, wherein the solid content of the positive electrode slurry was 72wt%.
  • the positive electrode slurry was evenly coated on the positive electrode collector to obtain a positive electrode film.
  • the obtained positive electrode film was dried at 85°C, cold pressed, cut into pieces, and cut, and then dried at 85°C under vacuum conditions for 4 hours to obtain a positive electrode sheet.
  • Polyethylene (PE) with a thickness of 9 ⁇ m was used as the separator;
  • the positive electrode sheet, the separator and the negative electrode sheet are stacked in order, so that the separator is placed between the positive electrode sheet and the negative electrode sheet to play an isolating role, and then wound to obtain an electrode assembly; the electrode assembly is placed in an outer packaging aluminum-plastic film, and the electrolyte prepared in step (1) is injected into the dried battery. After vacuum packaging, standing, forming, shaping and other processes, the preparation of the lithium-ion battery is completed.
  • capacity retention rate remaining discharge capacity/initial discharge capacity ⁇ 100%.
  • the battery cell is discharged quickly at room temperature and left for 5 minutes. Then it is charged normally, left for 5 minutes, and then discharged at 0.2C to 3.0V. The discharge capacity is recorded as the capacity at room temperature.
  • the discharge capacity of the battery cell to be tested is recorded as the normal temperature capacity; after being left for 5 minutes, normal charging is performed; after being left for 5 minutes, the battery is discharged at 2.0C to 3.0V, and the value of discharge capacity/normal temperature capacity is recorded.
  • the battery was placed in a -20°C thermostat, discharged at a constant current of 0.2C to 80% SOC, discharged at a current of 1.5A for 15s, and rested for 2s.
  • the cycle discharge-resting process was repeated until the battery voltage was lower than 3.0V, and the number of cycles was recorded.
  • the battery is fully charged at 20 ⁇ 5°C, the furnace temperature is set to 25°C, and after standing for 30 minutes, the temperature is increased at a rate of 5 ⁇ 2°C to the specified temperature °C ⁇ 2°C, and maintained for 60 minutes.
  • the temperature of the hot box is monitored during the process.
  • the battery cell was disassembled and immersed in DMC solution for several times to wash out the electrolyte and lithium salt. All solids were dried and weighed, and the liquid retention volume of the electrolyte/battery cell capacity was measured by differential weight method to obtain the value of the liquid retention coefficient.
  • Table 2 shows the performance parameters of the lithium-ion batteries provided in Examples 1 to 8 and Comparative Examples 1 to 4 of the present application.
  • Figure 4 shows the -20°C capacity retention rate of the batteries provided in Comparative Example 1 and Example 5, wherein Base is the battery in Comparative Example 1 and 1%A is the battery in Example 5.
  • Figure 5 shows the SOC-RSS curves of the batteries provided in Comparative Example 1 and Example 5, wherein Base is the battery in Comparative Example 1 and 1%A is the battery in Example 5.
  • doping 0.01 ⁇ m to 1 ⁇ m of solid electrolyte in the electrode can significantly improve the high-temperature cycle capacity retention rate, low-temperature capacity retention rate, low-temperature loading times, rate discharge performance and hot box temperature of lithium-ion batteries, and reduce the minimum liquid retention coefficient and high-temperature cycle expansion rate.
  • ethylene carbonate (EC), propylene carbonate (PC) and diethyl carbonate (DEC) are mixed uniformly in a mass ratio of 3:3:4 to obtain a non-aqueous solvent, and then fully dried lithium salt LiPF6 is dissolved in the non-aqueous solvent to make the mass percentage of LiPF6 in the electrolyte be 12.5%, and mixed uniformly to obtain an electrolyte.
  • a Cu foil with a thickness of 8 ⁇ m was used as the negative electrode current collector, and an Al foil with a thickness of 8 ⁇ m was used as the positive electrode current collector.
  • the negative electrode active material artificial graphite/Si composite material, the binder styrene butadiene rubber (abbreviated as SBR), and the thickener sodium carboxymethyl cellulose (abbreviated as CMC) are added to the solid electrolyte according to the weight ratio of 97.4:1.2:1.4 according to the formula shown in Table 3, and mixed, and fully stirred and mixed in an appropriate amount of deionized water to form a uniform negative electrode slurry; the slurry is coated on the negative electrode collector, dried, and cold pressed to obtain a negative electrode sheet.
  • Lithium cobalt oxide (LiCoO 2 ), conductive carbon black (Super P) and polyvinylidene fluoride were mixed at a mass ratio of 97:1.4:1.6, and 0.5wt% of solid electrolyte (Li 1.4 Al 0.4 Ti 1.6 (PO 4 ) 3 ) with a particle size of 0.2 ⁇ m was added, N-methylpyrrolidone (NMP) was added, and the mixture was stirred evenly using a vacuum mixer to obtain a positive electrode slurry, wherein the solid content of the positive electrode slurry was 72wt%.
  • the positive electrode slurry was evenly coated on the positive electrode collector to obtain a positive electrode film.
  • the obtained positive electrode film was dried at 85°C, cold pressed, cut into pieces, and cut, and then dried at 85°C under vacuum conditions for 4 hours to obtain a positive electrode sheet.
  • Polyethylene (PE) with a thickness of 9 ⁇ m was used as the separator;
  • the positive electrode sheet, the separator and the negative electrode sheet are stacked in order, so that the separator is placed between the positive electrode sheet and the negative electrode sheet to play an isolating role, and then wound to obtain an electrode assembly; the electrode assembly is placed in an outer packaging aluminum-plastic film, and the electrolyte prepared in step (1) is injected into the dried battery. After vacuum packaging, standing, forming, shaping and other processes, the preparation of the lithium-ion battery is completed.
  • the lithium ion batteries prepared in the above embodiments and comparative examples were subjected to performance tests.
  • the test methods were as described above.
  • the results are shown in Table 4, which shows the performance parameters of the lithium ion batteries provided in Examples 9 to 15 and Comparative Examples 5 to 8 of the present application.
  • doping 0.01 ⁇ m to 1 ⁇ m solid electrolyte in both the positive and negative electrodes can significantly improve the high-temperature cycle capacity retention rate, low-temperature capacity retention rate, low-temperature loading times, rate discharge performance and hot box temperature of lithium-ion batteries, and reduce the minimum liquid retention coefficient and high-temperature cycle expansion rate.
  • ethylene carbonate (EC), propylene carbonate (PC) and diethyl carbonate (DEC) are mixed uniformly in a mass ratio of 3:3:4 to obtain a non-aqueous solvent, and then fully dried lithium salt LiPF6 is dissolved in the non-aqueous solvent to make the mass percentage of LiPF6 in the electrolyte be 12.5%, and mixed uniformly to obtain an electrolyte.
  • a Cu foil with a thickness of 8 ⁇ m was used as the negative electrode current collector, and an Al foil with a thickness of 8 ⁇ m was used as the positive electrode current collector.
  • a negative electrode active material artificial graphite/Si composite material, a binder styrene-butadiene rubber (abbreviated as SBR), and a thickener sodium carboxymethyl cellulose (abbreviated as CMC) are mixed according to a weight ratio of 97.4:1.2:1.4, and 0.5wt% of a solid electrolyte ( Li1.4Al0.4Ti1.6 ( PO4 ) 3 ) with a particle size of 0.5 ⁇ m is added, and the mixture is fully stirred and mixed in an appropriate amount of deionized water to form a uniform negative electrode slurry; the slurry is coated on a negative electrode current collector, dried, and cold pressed to obtain a negative electrode sheet.
  • SBR binder styrene-butadiene rubber
  • CMC thickener sodium carboxymethyl cellulose
  • Lithium cobalt oxide (LiCoO 2 ), conductive carbon black (Super P) and polyvinylidene fluoride were mixed at a mass ratio of 97:1.4:1.6, and 0.5wt% of solid electrolyte (Li 1.4 Al 0.4 Ti 1.6 (PO 4 ) 3 ) with a particle size of 0.2 ⁇ m was added, N-methylpyrrolidone (NMP) was added, and the mixture was stirred evenly using a vacuum mixer to obtain a positive electrode slurry, wherein the solid content of the positive electrode slurry was 72wt%.
  • the positive electrode slurry was evenly coated on the positive electrode collector to obtain a positive electrode film.
  • the obtained positive electrode film was dried at 85°C, cold pressed, cut into pieces, and cut, and then dried at 85°C under vacuum conditions for 4 hours to obtain a positive electrode sheet.
  • Polyethylene (PE) with a thickness of 9 ⁇ m was used as a diaphragm.
  • the slurry shown in Table 5 was sprayed on the side of the diaphragm close to the positive electrode.
  • the slurry shown in Table 5 was sprayed on the side of the diaphragm close to the negative electrode.
  • the positive electrode sheet, the separator and the negative electrode sheet are stacked in order, so that the separator is placed between the positive electrode sheet and the negative electrode sheet to play an isolating role, and then wound to obtain an electrode assembly; the electrode assembly is placed in an outer packaging aluminum-plastic film, and the electrolyte prepared in step (1) is injected into the dried battery. After vacuum packaging, standing, forming, shaping and other processes, the preparation of the lithium-ion battery is completed.
  • the lithium ion batteries prepared in the above embodiments and comparative examples were subjected to performance tests.
  • the test methods were as above.
  • the results are shown in Table 6.
  • Table 6 shows the performance parameters of the lithium ion batteries provided in Examples 16 to 21 of the present application and Comparative Example 9.
  • ethylene carbonate (EC), propylene carbonate (PC) and diethyl carbonate (DEC) are mixed uniformly in a mass ratio of 3:3:4 to obtain a non-aqueous solvent, and then fully dried lithium salt LiPF6 is dissolved in the non-aqueous solvent to make the mass percentage of LiPF6 in the electrolyte be 12.5%, and mixed uniformly to obtain an electrolyte.
  • a Cu foil with a thickness of 8 ⁇ m was used as the negative electrode current collector, and an Al foil with a thickness of 8 ⁇ m was used as the positive electrode current collector; according to the formula shown in Table 1, the slurry with the formula shown in Table 7 was sprayed on the surface of the negative electrode current collector and the positive electrode current collector, respectively.
  • the slurry used NMP as a solvent included 0.1 wt% of a binder SBR and 10 wt% of a solid electrolyte with a D50 of 0.5 ⁇ m, and after drying, a 1 ⁇ m thick solid electrolyte coating was formed on the surface of the negative electrode current collector and the positive electrode current collector, respectively.
  • a negative electrode active material artificial graphite/Si composite material, a binder styrene-butadiene rubber (abbreviated as SBR), and a thickener sodium carboxymethyl cellulose (abbreviated as CMC) are mixed according to a weight ratio of 97.4:1.2:1.4, and 0.5wt% of a solid electrolyte ( Li1.4Al0.4Ti1.6 ( PO4 ) 3 ) with a particle size of 0.5 ⁇ m is added, and the mixture is fully stirred and mixed in an appropriate amount of deionized water to form a uniform negative electrode slurry; the slurry is coated on a negative electrode current collector, dried, and cold pressed to obtain a negative electrode sheet.
  • SBR binder styrene-butadiene rubber
  • CMC thickener sodium carboxymethyl cellulose
  • Lithium cobalt oxide (LiCoO 2 ), conductive carbon black (Super P) and polyvinylidene fluoride were mixed at a mass ratio of 97:1.4:1.6, and 0.5wt% of solid electrolyte (Li 1.4 Al 0.4 Ti 1.6 (PO 4 ) 3 ) with a particle size of 0.2 ⁇ m was added, N-methylpyrrolidone (NMP) was added, and the mixture was stirred evenly using a vacuum mixer to obtain a positive electrode slurry, wherein the solid content of the positive electrode slurry was 72wt%.
  • the positive electrode slurry was evenly coated on the positive electrode collector to obtain a positive electrode film.
  • the obtained positive electrode film was dried at 85°C, cold pressed, cut into pieces, and cut, and then dried at 85°C under vacuum conditions for 4 hours to obtain a positive electrode sheet.
  • Polyethylene (PE) with a thickness of 9 ⁇ m was used as the diaphragm, and the slurry with the formula shown in Table 8 was sprayed on both sides of the diaphragm.
  • the slurry used NMP as a solvent included 0.1 wt% of a binder SBR and 10 wt% of a solid electrolyte with a D50 of 0.5 ⁇ m. After drying, a solid electrolyte coating with a thickness of 1 ⁇ m was formed on both sides of the diaphragm.
  • the positive electrode sheet, the separator and the negative electrode sheet are stacked in order, so that the separator is placed between the positive electrode sheet and the negative electrode sheet to play an isolating role, and then wound to obtain an electrode assembly; the electrode assembly is placed in an outer packaging aluminum-plastic film, and the electrolyte prepared in step (1) is injected into the dried battery. After vacuum packaging, standing, forming, shaping and other processes, the preparation of the lithium-ion battery is completed.
  • the lithium-ion battery provided by the present invention can be used in consumer products, such as terminals, including mobile phones, watches, tablets, etc. Equipment; it can also be used in power products, such as automobiles, to improve the performance and battery life of products at low or high temperatures.

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Abstract

一种半固态锂电池，包括：电解液；设置在电解液中的隔膜；分别设置在隔膜两侧的正极极片和负极极片；正极极片包括正极集流体和设置在正极集流体上的正极活性层；正极活性层中掺杂有0.1wt％～5wt％的氧化物电解质，氧化物电解质的D50为0.05μm～1.2μm；负极极片包括负极集流体和设置在负极集流体上的负极活性层。在正极活性层中掺杂氧化物电解质，能够降低电池的最低保液系数和高温循环1000cls的膨胀率，提高电池高温循环1000cls的容量保持率、-20℃的容量保持率、-20℃拉载次数、2C/0.2C倍率放电容量和热箱温度等性能。

Description

半固态锂电池及包含其的终端
本申请要求于2023年9月27日提交中国国家知识产权局、申请号为202311262558.2、发明名称为“半固态锂电池及包含其的终端”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。
技术领域
本申请涉及电池技术领域，尤其涉及半固态锂电池及包含其的终端。
背景技术
锂离子电池的阻抗由欧姆内阻、SEI膜界面阻抗、电荷转移阻抗、离子扩散内阻等构成，随着电池能量密度的提升，电池的界面阻抗逐渐增加，电池的低温性能、高温性能等随之下降，导致移动电子设备续航时间减短。
发明内容
本申请提供了一种半固态锂电池及包含其的终端，本申请提供的半固态锂电池具有良好的高温性能、低温性能和大倍率放电容量，能够延长移动电子设备等终端在高温或低温下的续航时间。
本申请提供了一种半固态锂电池，包括：
电解液；
设置在所述电解液中的隔膜；
分别设置在所述隔膜两侧的正极极片和负极极片；
所述正极极片包括正极集流体和设置在所述正极集流体上的正极活性层；所述正极活性层中掺杂有0.1wt％～5wt％的氧化物电解质，所述氧化物电解质的D50为0.05μm～1.2μm；
所述负极极片包括负极集流体和设置在所述负极集流体上的负极活性层。
本申请将D50为0.05μm～1.2μm氧化物电解质以0.1wt％～5wt％的掺杂量添加到正极材料中形成正极活性层，能够降低电池的最低保液系数、将其由1.55g/Ah降至1.41g/Ah以下；降低高温循环1000cls的膨胀率，将其由15％降低至13.1％以下；提高电池高温循环1000cls的容量保持率，由58％提高至70％以上；提高-20℃的容量保持率，由50％左右提高至55％以上；提高-20℃拉载次数，由20次显著提升至50次以上；提高2C/0.2C倍率放电容量，但提高程度不明显；提高热箱温度，由126℃提高至130℃以上。而实验结果表明，氧化物电解质粒径过小或过大对上述性能均无明显改善作用，甚至有可能使上述性能，尤其是低温拉载次数变劣。
进一步的，本申请将D50为0.05μm～1.2μm氧化物电解质以0.1wt％～5wt％的掺杂量添加到负极材料中形成负极活性层，即正极活性层和负极活性层均掺杂氧化物电解质，能够进一步降低电池的最低保液系数，降低至1.35g/Ah以下；降低高温循环1000cls的膨胀 率，降低至12.2％以下；提高电池高温循环1000cls的容量保持率，提高至70％以上；提高-20℃的容量保持率，提高至60％以上；提高-20℃拉载次数，提高至60次以上；提高2C/0.2C倍率放电容量，提高至94％以上；提高热箱温度至132℃以上。而氧化物电解质粒径过小或过大对上述性能的进一步改善无明显作用，反而会影响在正极活性层中掺杂氧化物电解质带来的性能上的改进。
进一步的，本申请在隔膜的至少一侧，优选两侧设置有包括氧化物电解质的涂层，能够进一步降低电池的最低保液系数、降低至1.30g/Ah以下；降低高温循环1000cls的膨胀率，降低至11.5％以下；提高电池高温循环1000cls的容量保持率，提高至77％以上；提高-20℃的容量保持率，提高至65％以上；提高-20℃拉载次数，提高至90次以上；提高2C/0.2C倍率放电容量，提高至95％以上；提高热箱温度至134℃以上。
更进一步的，本申请在正极集流体与正极活性层和/或负极集流体与负极活性层之间设置包括氧化物电解质的涂层，进一步提高电池的安全性能，尤其是针刺安全和挤压安全。
本申请通过在正极活性层、负极活性层中引入D50为0.05μm～1.2μm的氧化电解质，进一步的在隔膜和集流体上形成含有氧化电解质的涂层，降低了电极/电解液界面的离子传输阻抗，使得正负极具有离子传输更快的界面，同时提升了电极/电解液界面稳定性，进而显著提升了电池的低温性能、倍率放电性能、高温性能以及安全性。本申请提供的锂离子电池可用于消费类产品，例如终端，包括手机、手表、平板等设备；也可以用于动力产品，例如汽车等，可以显著提高产品在低温和高温下的使用性能，延长其续航能力。
应当理解的是，本申请中对技术特征、技术方案、有益效果或类似语言的描述并不是暗示在任意的单个实施例中可以实现所有的特点和优点。相反，可以理解的是对于特征或有益效果的描述意味着在至少一个实施例中包括特定的技术特征、技术方案或有益效果。因此，本说明书中对于技术特征、技术方案或有益效果的描述并不一定是指相同的实施例。进而，还可以任何适当的方式组合本实施例中所描述的技术特征、技术方案和有益效果。本领域技术人员将会理解，无需特定实施例的一个或多个特定的技术特征、技术方案或有益效果即可实现实施例。在其他实施例中，还可在没有体现所有实施例的特定实施例中识别出额外的技术特征和有益效果。
附图说明
为了更清楚地说明本申请实施例的技术方法，下面将对实施例中所需使用的附图作以简单地介绍。
图1为本申请第一实施例提供的半固态锂电池的结构示意图；
图2为本申请第二实施例提供的半固态锂电池的结构示意图；
图3为本申请第三实施例提供的半固态锂电池的结构示意图；
图4为对比例1和实施例5提供的电池的-20℃容量保持率；
图5为对比例1和实施例5提供的电池的SOC-RSS曲线。
具体实施方式
在本申请实施例中，“示例性的”或者“例如”等词用于表示作例子、例证或说明。本 申请实施例中被描述为“示例性的”或者“例如”的任何实施例或设计方案不应被解释为比其它实施例或设计方案更优选或更具优势。确切而言，使用“示例性的”或者“例如”等词旨在以具体方式呈现相关概念。
除非另外定义，本申请使用的技术术语或者科学术语应当为本申请所属领域内具有一般技能的人士所理解的通常意义。本申请中使用的“第一”“第二”以及类似的词语并不表示任何顺序、数量或者重要性，而只是用来区分不同的组成部分。同样的，“一个”、“一”或“该”等类似词语也不表示数量限制，而是表示存在至少一个。“包括”或“包含”等类似的词语意指出现该词前面的元件或者物件涵盖出现在该词后面列举的元件或者物件及其等同，而不排除其他元件或者物件。“连接”或者“相连”等类似的词语并非限定于物理的或者机械的连接，而是可以包括电性的连接，不管是直接的还是间接的。“上”、“下”、“左”、“右”等仅用于表示相对位置关系，当被描述的对象的绝对位置改变后，则该相对位置关系也可能相应地改变。
本申请了一种半固态锂电池，包括：
电解液；
设置在所述电解液中的隔膜；
分别设置在所述隔膜两侧的正极极片和负极极片；
所述正极极片包括正极集流体和设置在所述正极集流体上的正极活性层；所述正极活性层中掺杂有0.1wt％～5wt％的氧化物电解质，所述氧化物电解质的D50为0.05μm～1.2μm；
所述负极极片包括负极集流体和设置在所述负极集流体上的负极活性层。
参见图1，图1为本申请第一实施例提供的半固态锂电池的结构示意图，其中，11为电解液，12为隔膜，13为正极集流体，14为正极活性层，15为负极集流体，16为负极活性层。
本申请提供的半固态锂电池包括电解液11，所述电解液为非水溶剂电解液，包括非水溶剂、锂盐和可选的添加剂。所述非水溶剂包括环状碳酸酯与链状碳酸酯，在一些具体的实现方式中，所述环状碳酸酯包括但不限于碳酸乙烯酯(EC)或碳酸丙烯酯(PC)中的一种或多种，所述链状碳酸酯包括但不限于碳酸二甲酯(DMC)、碳酸二乙酯(DEC)和碳酸甲乙酯(EMC)中的一种或多种。在一些可能的实现方式中，所述非水溶剂包括碳酸乙烯酯、碳酸丙烯酯和碳酸二乙酯，碳酸乙烯酯、碳酸丙烯酯和碳酸二乙酯的质量比优选为1～5:1～5：1～5，更优选为3:3:4。所述锂盐为电解质，包括但不限于六氟磷酸锂、二氟草酸硼酸锂、二氟磷酸锂(LiPO2F2)和二氟磺酰亚胺锂(LiFSI)中的一种或多种，优选为六氟磷酸锂。所述锂盐在电解液中的浓度优选为10wt％～20wt％，更优选为12.5wt％～16wt％。本申请对所述添加剂的种类和用量没有特殊限制，按照电池功能进行选择即可，本申请对此不再进行赘述。
本申请提供的半固态锂电池包括设置在电解液11中的隔膜12，隔膜12用于将正极极片和负极极片隔离。本申请对所述隔膜的材质、厚度均没有特殊限制，本领域常用的隔膜即可，例如9μm厚的PE隔膜。
本申请提供的半固态电池中，正极极片设置在隔膜12一侧，负极极片设置在隔膜12 另一侧。正极极片包括正极集流体13和设置在所述正极集流体上的正极活性层14，本申请对所述正极集流体13没有特殊限制，本领域技术人员熟知的正极集流体即可，例如厚度为8μm的铝箔等。
本申请在正极活性层中掺杂0.1wt％～5wt％、D50为0.05μm～1.2μm的氧化物电解质，能够降低电池的最低保液系数，降低高温循环1000cls的膨胀率，提高电池高温循环1000cls的容量保持率，提高-20℃的容量保持率，提高-20℃拉载次数，提高2C/0.2C倍率放电容量，提高热箱温度。实验结果表明，氧化物电解质粒径过小，例如小于10nm，或过大，例如大于1.5μm，对上述性能均无明显改善作用，甚至有可能使上述性能，尤其是低温拉载次数变劣。在一些具体的实现方式中，所述正极活性层包括正极活性材料、导电剂、粘结剂和氧化物电解质，其中正极活性材料包括但不限于三元正极材料、钴酸锂、富锰锂、镍锰尖晶石、磷酸铁锂、磷酸铁锰锂、锰酸锂中的一种或多种；其中，三元正极材料的化学式可以为LiNixCoyMn1-x-yO2，0.7＜x＜1，0＜y＜0.3。导电剂包括但不限于导电炭黑、乙炔黑、科琴黑、导电石墨、导电碳纤维、碳纳米管、金属粉、碳纤维中的一种或多种；粘结剂包括但不限于丁苯橡胶(Polymerized Styrene Butadiene Rubber，SBR)、羧甲基纤维素(Carboxymethyl Cellulose，CMC)、聚偏氟乙烯(Poly(vinylidene fluoride)，PVDF)、聚甲基丙烯酸甲酯(Polymethyl Methacrylate，PMMA)、聚丙烯腈(Polyacrylonitrile，PAN)、聚氧化乙烯(Polyethylene Oxide，PEO)中的一种或多种。在一些具体的实现方式中，所述正极活性材料、导电剂和粘结剂的质量比为70～99：0.5～15：0.5～15，优选为75～99:1～10：1～10，更优选为80～99:1～5:1～5。
在一些具体的实现方式中，所述正极活性层中掺杂有0.1wt％～5wt％的氧化物电解质，即所述氧化物电解质占正极活性材料、导电剂和粘结剂总量的0.1wt％～5wt％，优选为0.2wt％～4wt％，更优选为0.5wt％～3wt％。所述氧化物电解质的D50为0.05μm～1.2μm，优选为0.08μm～1μm，更优选为0.1μm～1μm。所述氧化物电解质可以选自NASICON结构材料、钙钛矿结构材料、反钙钛矿结构材料、LISICON结构和石榴石结构材料中的一种或多种，包括但不限于Li1.4Al0.4Ti1.6(PO4)3、Li1.5Al0.5Ge1.5(PO4)3、Li7La3Zr2O12、Li6.4La3Zr2Ta0.6O12和La0.56Li0.33TiO3等，优选为Li1.4Al0.4Ti1.6(PO4)3或Li7La3Zr2O12。
在一些具体的实现方式中，所述负极极片包括负极集流体15和设置在所述负极集流体15上的负极活性层16。本申请对所述负极集流体15没有特殊限制，本领域技术人员熟知的负极集流体即可，例如厚度为8μm的铜箔等。
在一些具体的实现方式中，所述负极活性层包括负极活性材料、导电剂和粘结剂，其中，负极活性材料包括但不限于碳材料、硅基材料、金属锂或锂合金中的一种或多种，优选为石墨或硅基材料中的一种或两种；导电剂包括但不限于导电炭黑、乙炔黑、科琴黑、导电石墨、导电碳纤维、碳纳米管、金属粉、碳纤维中的一种或多种；粘结剂包括但不限于丁苯橡胶(Polymerized Styrene Butadiene Rubber，SBR)、羧甲基纤维素(Carboxymethyl Cellulose，CMC)、聚偏氟乙烯(Poly(vinylidene fluoride)，PVDF)、聚甲基丙烯酸甲酯(Polymethyl Methacrylate，PMMA)、聚丙烯腈(Polyacrylonitrile，PAN)、聚氧化乙烯(Polyethylene Oxide，PEO)中的一种或多种。在一些具体的实现方式中，所述负极活性材料、导电剂和粘结剂的质量比为70～99：0.5～15：0.5～15，优选为75～99:1～10：1～10，更优选为 80～99:1～5:1～5。
在一些具体的实现方式中，本申请在负极活性层中掺杂0.1wt％～5wt％、D50为0.05μm～1.2μm的氧化物电解质，进一步降低电池的最低保液系数，降低高温循环1000cls的膨胀率，提高电池高温循环1000cls的容量保持率，提高-20℃的容量保持率，提高-20℃拉载次数，提高2C/0.2C倍率放电容量，提高热箱温度。实验结果表明，氧化物电解质粒径过小，例如小于10nm，或过大，例如大于1.5μm，对上述性能均无明显改善作用，甚至有可能使上述性能，尤其是低温拉载次数变劣。
在一些具体的实现方式中，所述负极活性层中掺杂有0.1wt％～5wt％的氧化物电解质，即所述氧化物电解质占负极活性材料、导电剂和粘结剂总量的0.1wt％～5wt％，优选为0.2wt％～4wt％，更优选为0.5wt％～3wt％。所述氧化物电解质的D50为0.05μm～1.2μm，优选为0.08μm～1μm，更优选为0.1μm～1μm。所述氧化物电解质可以选自NASICON结构材料、钙钛矿结构材料、反钙钛矿结构材料、LISICON结构和石榴石结构材料中的一种或多种，包括但不限于Li1.4Al0.4Ti1.6(PO4)3、Li1.5Al0.5Ge1.5(PO4)3、Li7La3Zr2O12、Li6.4La3Zr2Ta0.6O12和La0.56Li0.33TiO3等，优选为Li1.4Al0.4Ti1.6(PO4)3或Li7La3Zr2O12。
在一些具体的实现方式中，所述隔膜的至少一侧设置有包括氧化物电解质的涂层，参见图2，图2为本申请第二实施例提供的半固态锂电池的结构示意图，其中，21为电解液，22为隔膜，23为正极集流体，24为正极活性层，25为负极集流体，26为负极活性层,221为第一涂层，222为第二涂层。
本申请在隔膜的至少一侧设置包含固体氧化物的涂层，能够进一步降低电池的最低保液系数、降低至1.30g/Ah以下；降低高温循环1000cls的膨胀率，降低至11.5％以下；提高电池高温循环1000cls的容量保持率，提高至77％以上；提高-20℃的容量保持率，提高至65％以上；提高-20℃拉载次数，提高至90次以上；提高2C/0.2C倍率放电容量，提高至95％以上；提高热箱温度至134℃以上。
第二实施例提供的半固态锂电池中，电解液21，隔膜22，正极集流体23，正极活性层24，负极集流体25和负极活性层26参见上文所述，本申请在此不再赘述。
在一些具体的实现方式中，第一涂层221包括氧化物电解质和粘结剂，所述固体氧化物电解质和粘结剂的质量比优选为0.05～0.5:5～15，更优选为0.1～0.2:8～12。第一涂层221的厚度优选为0.5μm-5μm，更优选为1μm-2μm。所述氧化物电解质和粘结剂如上所述，本申请在此不再赘述。同样的，第二涂层222与第一涂层221相似，其可以相同，也可以不同，本申请在此不再赘述。
更进一步的，本申请在正极集流体与正极活性层和/或负极集流体与负极活性层之间设置包括氧化物电解质的涂层，进一步提高电池的安全性能，尤其是针刺安全和挤压安全。参见图3，图3为本申请第三实施例提供的半固态锂电池的结构示意图，其中，31为电解液，32为隔膜，33为正极集流体，34为正极活性层，35为负极集流体，36为负极活性层,321为第一涂层，322为第二涂层,331为第三涂层，351为第四涂层。
第三实施例提供的半固态锂电池中，电解液31，隔膜32，正极集流体33，正极活性层34，负极集流体35、负极活性层36、第一涂层321、第二涂层322参见上文所述，本申请在此不再赘述。
在一些具体的实现方式中，第三涂层331包括氧化物电解质和粘结剂，所述固体氧化物电解质和粘结剂的质量比优选为0.05～0.5:5～15，更优选为0.1～0.2:8～12。第三涂层331的厚度优选为0.5μm-5μm，更优选为1μm-2μm。所述氧化物电解质和粘结剂如上所述，本申请在此不再赘述。同样的，第四涂层351与第三涂层331相似，其可以相同，也可以不同，本申请在此不再赘述。
在一些具体的实现方式中，本发明在所述正极集流体远离正极活性层的一侧设置有包括氧化物电解质的第五涂层，和/或，在所述负极集流体远离负极活性层的一侧设置有包括氧化物电解质的第六涂层。第五涂层和第六涂层与第一涂层相似，本申请在此不再赘述。
在一些具体的实现方式中，所述正极活性层中掺杂有0.15wt％～3.5wt％的氧化物电解质，所述氧化物电解质的D50为0.05μm～1μm；所述氧化物电解质选自Li1.4Al0.4Ti1.6(PO4)3或Li7La3Zr2O12。
在一些具体的实现方式中，所述负极活性层中掺杂有0.15wt％～3.5wt％的氧化物电解质，所述氧化物电解质的D50为0.05μm～1μm；所述氧化物电解质选自Li1.4Al0.4Ti1.6(PO4)3。
在一些具体的实现方式中，所述第一涂层和第二涂层中，所述氧化物电解质的D50独立地为0.05μm～1.2μm；所述氧化物电解质独立地选自Li1.4Al0.4Ti1.6(PO4)3或Li7La3Zr2O12。
在一些具体的实现方式中，所述第三涂层和第四涂层中，所述氧化物电解质的D50独立地为0.05μm～1.2μm；所述氧化物电解质独立地选自Li1.4Al0.4Ti1.6(PO4)3或Li7La3Zr2O12。
在一些具体的实现方式中，所述第五涂层和第六涂层中，所述氧化物电解质的D50独立地为0.05μm～1.2μm；所述氧化物电解质独立地选自Li1.4Al0.4Ti1.6(PO4)3或Li7La3Zr2O12。
在一些具体的实现方式中，本申请提供的半固态锂电池具有如下性能参数：最低保液系数为1.25～1.45g/Ah；高温循环1000cls容量保持率为65％以上；高温循环1000cls的膨胀率为14％以下；-20℃容量保持率为55％以上；-20℃拉载次数为45次以上；2C/0.2C倍率放电容量为92％以上；热箱温度为130℃以上。
本发明还提供了上述半固态锂电池的制备方法，包括以下步骤：
将包括正极活性材料、导电剂、粘结剂和氧化物电解质的正极浆料在正极集流体上形成正极活性层，得到正极极片；在包括负极活性材料、导电剂和粘结剂的负极浆料在负极集流体上形成负极活性层，得到负极极片；
将正极极片、负极极片、隔膜和电解液组装半固态锂电池。
在一些具体的实现方式中，所述正极浆料可以按照以下方法制备：
将正极活性材料、导电剂、粘结剂、氧化物电解质和溶剂混合，得到正极浆料。
在一些具体的实现方式中，所述正极浆料可以按照以下方法制备：
将氧化物电解质和正极活性材料进行预烧结，得到氧化物电解质/正极活性材料复合物；
将所述复合物、粘结剂、导电剂和溶剂混合，得到正极浆料。
在一些具体的实现方式中，所述预烧结的温度不大于400℃，优选为200～400℃。首先将氧化物电解质和正极活性材料进行预烧结，能够是氧化物电解质和正极活性材料混合更均匀，从而进一步提高电池的性能。
得到正极浆料后，将正极浆料涂覆在正极集流体上，烘干、冷压、裁片、分切、干燥后得到正极极片。
在一些具体的实现方式中，所述负极浆料还包括氧化物电解质，所述负极极片的制备方法与正极极片的制备方法相似，本申请在此不再赘述。
在一些具体的实现方式中，在隔膜的至少一侧优选两侧形成含有氧化物电解质的涂层，其制备方法如下：
将含有氧化物电解质和粘结剂的浆料涂覆在隔膜表面，烘干、冷压后形成涂层。
本申请对所述涂覆的方法没有特殊限制，可以通过喷涂、凹版印刷等方式进行涂覆。
在一些具体的实现方式中，在形成正极活性层或负极活性层之前，还包括在正极集流体或负极集流体上形成包含氧化物电解质的涂层的步骤，可以在正极集流体朝向正极活性层的一侧或负极集流体朝向负极活性层的一侧形成涂层，也可以在正极集流体或负极集流体的两侧形成涂层。形成涂层的方法如上所述，本申请在此不再赘述。
本申请提供的半固态锂离子电池可用于消费类产品，例如终端，包括手机、手表、平板等设备；也可以用于动力产品，例如汽车等，可提高产品在低温或高温下的使用性能和电池续航能力。
基于此，本申请还提供了一种终端，包括上述技术方案所述的半固态锂电池。本领域技术人员可以理解的是，本申请提及的终端可以是任何具备通信和存储功能的设备，例如智能手机、蜂窝电话、无绳电话、会话启动协议(Session Initiation Protocol，SIP)电话、平板电脑、个人数字处理(Personal Digital Assistant,PAD)、笔记本电脑、数码相机、电子书籍阅读器、便携多媒体播放器、具有无线通信功能的手持设备、计算设备或连接到无线调制解调器的其他处理设备、车载设备、可穿戴设备、5G终端设备等，本申请实施例对此并不限定。
以下结合实施例对本申请提供的锂离子电池及其制备方法进行详细描述。
实施例1～8及比较例1～4
(1)电解液的制备
在含水量<10ppm的氩气气氛手套箱中，将碳酸乙烯酯(EC)、碳酸丙烯酯(PC)及碳酸二乙酯(DEC)按照3:3:4的质量比混合均匀得到非水溶剂，再将充分干燥的锂盐LiPF6溶解于上述非水溶剂，使电解液中LiPF6的质量百分含量为12.5％，混合均匀，获得电解液。
(2)集流体的制备
以厚度为8μm的Cu箔材为负极集流体，以厚度为8μm的Al箔材为正极集流体。
(3)负极极片的制备
将负极活性材料人造石墨/Si复合材料、粘结剂丁苯橡胶(SBR)、增稠剂羧甲基纤维素钠(CMC)按照重量比97.4:1.2:1.4进行混合，在适量的去离子水中充分搅拌混合，形成均匀的负极浆料；将所述浆料涂覆于负极集流体上，烘干、冷压，得到负极极片。
(4)正极极片的制备
将钴酸锂(LiCoO2)、导电炭黑(Super P)和聚偏二氟乙烯按照97:1.4:1.6的质量比，按照表1所示配方加入固体电解质进行混合，加入N-甲基吡咯烷酮(NMP)，使用真空搅拌机搅拌均匀，制得正极浆料，其中正极浆料的固含量为72wt％。将正极浆料均匀涂覆于正极集流体上，制成正极膜片。将制得的正极膜片在85℃下烘干、冷压、裁片、分切，然后在85℃的真空条件下干燥4小时，得到正极极片。
表1实施例1～8及比较例1～4提供的锂离子电池正极配方
(5)隔膜的制备
采用厚度为9μm的聚乙烯(PE)作为隔膜；
(6)锂离子电池的制备
将正极极片、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之间起到隔离的作用，然后卷绕得到电极组件；将电极组件置于外包装铝塑膜中，将步骤(1)制备好的电解液注入到干燥后的电池中，经过真空封装、静置、化成、整形等工序，即完成锂离子电池的制备。
对上述实施例和比较例制备的锂离子电池进行性能测试，测试方法如下：
(1)锂离子电池循环测试方法
将电池放至45℃恒温箱中，以恒定电流1.5C充电至4.48V，4.48V下恒压充电至0.05C，再以1.0C恒流放电至3.0V，此次为一个充放电循环过程，按上述方式进行1000次循环充放电测试，监控容量保持率和电芯厚度膨胀率。
其中，容量保持率＝剩余放电容量/初始放电容量×100％。
(2)低温放电容量
常温条件下电芯快速放电，搁置5min；再进行常规充电，搁置5分钟后，以0.2C放电至3.0V，记录此次放电容量为常温容量。
放电后搁置5分钟，再进行常规充电，在-20±2℃条件下搁置2h后，以0.2C电流放电至截止电压3.0V。记录放电容量/常温容量的值。
(3)倍率放电容量
待测电芯测试的放电容量记录为常温容量；搁置5min后，进行常规充电；搁置5min，2.0C放电至3.0V，记录放电容量/常温容量的值。
(4)低温拉载次数
将电池放至-20℃恒温箱中，以恒定电流0.2C放电至80％SOC，以1.5A电流放电15s，静置2s。循环放电-静置过程，直到电池电压低于3.0V，记录循环次数。
(5)锂离子电池热箱测试方法
电池20±5℃满充，设置炉温25℃，静置30min后开始以5±2℃升温速率，升温至指定温度℃±2℃，保持60min，监控过程中的热箱温度。
(6)电芯保液系数测试方法
将电芯拆解，浸泡在DMC溶液中，浸泡数次，洗出电解液和锂盐，将所有固体烘干后称重，通过差重法测得电解液的保液量/电芯容量得到保液系数的值。
结果参见表2、图4和图5，表2为本申请实施例1～8及对比例1～4提供的锂离子电池的性能参数，图4为对比例1和实施例5提供的电池的-20℃容量保持率，其中，Base为对比例1电池，1％A为实施例5电池；图5为对比例1和实施例5提供的电池的SOC-RSS曲线，其中，Base为对比例1电池，1％A为实施例5电池。
表2本申请实施例1～8及对比例1～4提供的锂离子电池的性能参数
由表2可知，在电极中掺杂0.01μm～1μm的固态电解质能够显著提高锂离子电池的高温循环容量保持率、低温容量保持率、低温拉载次数、倍率放电性能和热箱温度，降低最低保液系数和高温循环膨胀率。
实施例9～15及对比例5～8
(1)电解液的制备
在含水量<10ppm的氩气气氛手套箱中，将碳酸乙烯酯(EC)、碳酸丙烯酯(PC)及碳酸二乙酯(DEC)按照3:3:4的质量比混合均匀得到非水溶剂，再将充分干燥的锂盐LiPF6溶解于上述非水溶剂，使电解液中LiPF6的质量百分含量为12.5％，混合均匀，获得电解液。
(2)集流体的制备
以厚度为8μm的Cu箔材为负极集流体，以厚度为8μm的Al箔材为正极集流体。
(3)负极极片的制备
将负极活性材料人造石墨/Si复合材料、粘结剂丁苯橡胶(简写为SBR)、增稠剂羧甲基纤维素钠(简写为CMC)按照重量比97.4:1.2:1.4，按照表3所示配方加入固体电解质进行混合，在适量的去离子水中充分搅拌混合，形成均匀的负极浆料；将所述浆料涂覆于负极集流体上，烘干、冷压，得到负极极片。
表3实施例9～15及比较例5～8提供的锂离子电池负极配方
(4)正极极片的制备
将钴酸锂(LiCoO2)、导电炭黑(Super P)和聚偏二氟乙烯按照97:1.4:1.6的质量比，加入0.5wt％、粒径为0.2μm的固体电解质(Li1.4Al0.4Ti1.6(PO4)3)进行混合，加入N-甲基吡咯烷酮(NMP)，使用真空搅拌机搅拌均匀，制得正极浆料，其中正极浆料的固含量为72wt％。将正极浆料均匀涂覆于正极集流体上，制成正极膜片。将制得的正极膜片在85℃下烘干、冷压、裁片、分切，然后在85℃的真空条件下干燥4小时，得到正极极片。
(5)隔膜的制备
采用厚度为9μm的聚乙烯(PE)作为隔膜；
(6)锂离子电池的制备
将正极极片、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之间起到隔离的作用，然后卷绕得到电极组件；将电极组件置于外包装铝塑膜中，将步骤(1)制备好的电解液注入到干燥后的电池中，经过真空封装、静置、化成、整形等工序，即完成锂离子电池的制备。
对上述实施例和比较例制备的锂离子电池进行性能测试，测试方法如上所述，结果参见表4，表4为本申请实施例9～15及对比例5～8提供的锂离子电池的性能参数。
表4本申请实施例9～15及对比例5～8提供的锂离子电池的性能参数
由表4可知，在正极和负极中同时掺杂0.01μm～1μm的固态电解质能够显著提高锂离子电池的高温循环容量保持率、低温容量保持率、低温拉载次数、倍率放电性能和热箱温度，降低最低保液系数和高温循环膨胀率。
实施例16～21及对比例9
(1)电解液的制备
在含水量<10ppm的氩气气氛手套箱中，将碳酸乙烯酯(EC)、碳酸丙烯酯(PC)及碳酸二乙酯(DEC)按照3:3:4的质量比混合均匀得到非水溶剂，再将充分干燥的锂盐LiPF6溶解于上述非水溶剂，使电解液中LiPF6的质量百分含量为12.5％，混合均匀，获得电解液。
(2)集流体的制备
以厚度为8μm的Cu箔材为负极集流体，以厚度为8μm的Al箔材为正极集流体。
(3)负极极片的制备
将负极活性材料人造石墨/Si复合材料、粘结剂丁苯橡胶(简写为SBR)、增稠剂羧甲基纤维素钠(简写为CMC)按照重量比97.4:1.2:1.4，加入0.5wt％、粒径为0.5μm的固体电解质(Li1.4Al0.4Ti1.6(PO4)3)进行混合，在适量的去离子水中充分搅拌混合，形成均匀的负极浆料；将所述浆料涂覆于负极集流体上，烘干、冷压，得到负极极片。
(4)正极极片的制备
将钴酸锂(LiCoO2)、导电炭黑(Super P)和聚偏二氟乙烯按照97:1.4:1.6的质量比，加入0.5wt％、粒径为0.2μm的固体电解质(Li1.4Al0.4Ti1.6(PO4)3)进行混合，加入N-甲基吡咯烷酮(NMP)，使用真空搅拌机搅拌均匀，制得正极浆料，其中正极浆料的固含量为72wt％。将正极浆料均匀涂覆于正极集流体上，制成正极膜片。将制得的正极膜片在85℃下烘干、冷压、裁片、分切，然后在85℃的真空条件下干燥4小时，得到正极极片。
(5)隔膜的制备
采用厚度为9μm的聚乙烯(PE)作为隔膜，在隔膜靠近正极的一侧喷涂表5所示的浆料，所述浆料以NMP为溶剂，包括0.1wt％的粘结剂SBR和10wt％、D50为0.5μm的固态电解质，在隔膜靠近负极的一侧喷涂表5所示的浆料，所述浆料以水为溶剂，包括0.1wt％的粘结剂SBR和10wt％的固态电解质，干燥后分别在隔膜两侧形成厚度为1μm的固态电解质涂层。
表5实施例及比较例提供的隔膜靠近正极的涂层配方
(6)锂离子电池的制备
将正极极片、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之间起到隔离的作用，然后卷绕得到电极组件；将电极组件置于外包装铝塑膜中，将步骤(1)制备好的电解液注入到干燥后的电池中，经过真空封装、静置、化成、整形等工序，即完成锂离子电池的制备。
对上述实施例和比较例制备的锂离子电池进行性能测试，测试方法如上，结果参见表6，表6为本申请实施例16～21及对比例9提供的锂离子电池的性能参数。
表6本申请实施例16～21及对比例9提供的锂离子电池的性能参数
由表6可知，在正极和负极中同时掺杂0.01μm～1μm的固态电解质，同时在隔膜两侧形成固态电解质层能够显著提高锂离子电池的高温循环容量保持率、低温容量保持率、低温拉载次数、倍率放电性能和热箱温度，降低最低保液系数和高温循环膨胀率。
实施例22～23及对比例10
(1)电解液的制备
在含水量<10ppm的氩气气氛手套箱中，将碳酸乙烯酯(EC)、碳酸丙烯酯(PC)及碳酸二乙酯(DEC)按照3:3:4的质量比混合均匀得到非水溶剂，再将充分干燥的锂盐LiPF6溶解于上述非水溶剂，使电解液中LiPF6的质量百分含量为12.5％，混合均匀，获得电解液。
(2)集流体的制备
以厚度为8μm的Cu箔材为负极集流体，以厚度为8μm的Al箔材为正极集流体；按照表1所示的配方，分别在负极集流体和正极集流体表面喷涂表7所示配方的浆料，所述浆料以NMP为溶剂，包括0.1wt％的粘结剂SBR和10wt％、D50为0.5μm的固态电解质，干燥后分别在负极集流体和正极集流体表面形成1μm厚的固态电解质涂层。
表7实施例及比较例提供的锂离子电池集流体涂层配方
(3)负极极片的制备
将负极活性材料人造石墨/Si复合材料、粘结剂丁苯橡胶(简写为SBR)、增稠剂羧甲基纤维素钠(简写为CMC)按照重量比97.4:1.2:1.4，加入0.5wt％、粒径为0.5μm的固体电解质(Li1.4Al0.4Ti1.6(PO4)3)进行混合，在适量的去离子水中充分搅拌混合，形成均匀的负极浆料；将所述浆料涂覆于负极集流体上，烘干、冷压，得到负极极片。
(4)正极极片的制备
将钴酸锂(LiCoO2)、导电炭黑(Super P)和聚偏二氟乙烯按照97:1.4:1.6的质量比，加入0.5wt％、粒径为0.2μm的固体电解质(Li1.4Al0.4Ti1.6(PO4)3)进行混合，加入N-甲基吡咯烷酮(NMP)，使用真空搅拌机搅拌均匀，制得正极浆料，其中正极浆料的固含量为72wt％。将正极浆料均匀涂覆于正极集流体上，制成正极膜片。将制得的正极膜片在85℃下烘干、冷压、裁片、分切，然后在85℃的真空条件下干燥4小时，得到正极极片。
(5)隔膜的制备
采用厚度为9μm的聚乙烯(PE)作为隔膜，在隔膜两侧分别喷涂表8所示配方的浆料所述浆料以NMP为溶剂，包括0.1wt％的粘结剂SBR和10wt％、D50为0.5μm的固态电解质，干燥后分别在隔膜两侧形成厚度为1μm的固态电解质涂层。
表8实施例及比较例提供的锂离子隔膜涂层配方
(6)锂离子电池的制备
将正极极片、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之间起到隔离的作用，然后卷绕得到电极组件；将电极组件置于外包装铝塑膜中，将步骤(1)制备好的电解液注入到干燥后的电池中，经过真空封装、静置、化成、整形等工序，即完成锂离子电池的制备。
对上述实施例和比较例制备的锂离子电池进行性能测试，测试方法如上，结果参见表9，表9为本申请实施例22～23及对比例10提供的锂离子电池的性能参数。
表9本申请实施例22～23及对比例10提供的锂离子电池的性能参数
由表9可知，在集流体上形成固态电解质层，能够显著提高电池的针刺安全和挤压安全性能。
本发明提供的锂离子电池可以用于消费类产品，例如终端，包括手机、手表、平板等 设备；也可以用于动力产品，例如汽车等，可提高产品在低温或高温下的使用性能和电池续航能力。
以上所述，仅为本申请的具体实施方式，但本申请的保护范围并不局限于此，任何在本申请揭露的技术范围内的变化或替换，都应涵盖在本申请的保护范围之内。因此，本申请的保护范围应以所述权利要求的保护范围为准。

Claims (21)

  1. 一种半固态锂电池，包括：
    电解液；
    设置在所述电解液中的隔膜；
    分别设置在所述隔膜两侧的正极极片和负极极片；
    所述正极极片包括正极集流体和设置在所述正极集流体上的正极活性层；所述正极活性层中掺杂有0.1wt％～5wt％的氧化物电解质，所述氧化物电解质的D50为0.05μm～1.2μm；
    所述负极极片包括负极集流体和设置在所述负极集流体上的负极活性层。
  2. 根据权利要求1所述的半固态锂电池，其特征在于，所述负极活性层中掺杂有0.1wt％～5wt％的氧化物电解质，所述氧化物电解质的D50为0.05μm～1.2μm。
  3. 根据权利要求1或2所述的半固态锂电池，其特征在于，所述隔膜的至少一侧设置有涂层，所述涂层包括氧化物电解质。
  4. 根据权利要求3所述的半固态锂电池，其特征在于，所述隔膜朝向正极极片的一侧设置有第一涂层，朝向负极极片的一侧设置有第二涂层。
  5. 根据权利要求4所述的半固态锂电池，其特征在于，所述第一涂层和第二涂层的厚度独立地为0.5μm-5μm；
    所述第一涂层和第二涂层中，氧化物电解质的D50独立地为0.05μm～1.2μm。
  6. 根据权利要求1～2任意一项所述的半固态锂电池，其特征在于，所述正极极片中，所述正极集流体和正极活性层之间设置有第三涂层，所述第三涂层包括氧化物电解质。
  7. 根据权利要求6所述的半固态锂电池，其特征在于，所述正极集流体远离正极活性层的一侧设置有第四涂层，所述第四涂层包括氧化物电解质。
  8. 根据权利要求7所述的半固态锂电池，其特征在于，所述第三涂层和第四涂层的厚度独立地为0.5μm-5μm；
    所述第三涂层和第四涂层中，氧化物电解质的D50独立地为0.05μm～1.2μm。
  9. 根据权利要求1～2任意一项所述的半固态锂电池，其特征在于，所述负极极片中，所述负极集流体和负极活性层之间设置有第五涂层，所述第五涂层包括氧化物电解质。
  10. 根据权利要求9所述的半固态锂电池，其特征在于，所述负极集流体远离负极活性层的一侧设置有第六涂层，所述第六涂层包括氧化物电解质。
  11. 根据权利要求9所述的半固态锂电池，其特征在于，所述第五涂层和第六涂层的厚度独立地为0.5μm-5μm；
    所述第五涂层和第六涂层中，氧化物电解质的D50独立地为0.05μm～1.2μm。
  12. 根据权利要求1～2任意一项所述的半固态锂电池，其特征在于，所述氧化物电解质选自NASICON结构材料、钙钛矿结构材料、反钙钛矿结构材料、LISICON结构和石榴石结构材料中的一种或多种。
  13. 根据权利要求12所述的半固态锂电池，其特征在于，所述氧化物电解质选自Li1.4Al0.4Ti1.6(PO4)3、Li1.5Al0.5Ge1.5(PO4)3、Li7La3Zr2O12、Li6.4La3Zr2Ta0.6O12和La0.56Li0.33TiO3 中的一种或多种。
  14. 根据权利要求13所述的半固态锂电池，其特征在于，所述正极活性层中的正极活性材料选自钴酸锂、富锰锂、镍锰尖晶石、磷酸铁锂、磷酸铁锰锂、锰酸锂中的一种或多种；
    所述负极活性层中的负极活性材料选自碳材料、硅基材料、金属锂、锂合金中的一种或多种。
  15. 根据权利要求14所述的半固态锂电池，其特征在于，所述正极活性层中掺杂有0.15wt％～3.5wt％的氧化物电解质，所述氧化物电解质的D50为0.05μm～1μm；所述氧化物电解质选自Li1.4Al0.4Ti1.6(PO4)3或Li7La3Zr2O12。
  16. 根据权利要求15所述的半固态锂电池，其特征在于，所述负极活性层中掺杂有0.15wt％～3.5wt％的氧化物电解质，所述氧化物电解质的D50为0.05μm～1μm；所述氧化物电解质选自Li1.4Al0.4Ti1.6(PO4)3。
  17. 根据权利要求16所述的半固态锂电池，其特征在于，所述隔膜朝向正极极片的一侧设置有第一涂层，朝向负极极片的一侧设置有第二涂层，所述第一涂层包括氧化物电解质，所述第二涂层包括氧化物电解质；
    所述第一涂层和第二涂层中，所述氧化物电解质的D50独立地为0.05μm～1.2μm；所述氧化物电解质独立地选自Li1.4Al0.4Ti1.6(PO4)3或Li7La3Zr2O12。
  18. 根据权利要求17所述的半固态锂电池，其特征在于，所述正极极片中，所述正极集流体和正极活性层之间设置有第三涂层，所述第三涂层包括氧化物电解质；所述正极集流体远离正极活性层的一侧设置有第四涂层，所述第四涂层包括氧化物电解质；
    所述第三涂层和第四涂层中，所述氧化物电解质的D50独立地为0.05μm～1.2μm；所述氧化物电解质独立地选自Li1.4Al0.4Ti1.6(PO4)3或Li7La3Zr2O12。
  19. 根据权利要求18所述的半固态锂电池，其特征在于，所述负极极片中，所述负极集流体和负极活性层之间设置有第五涂层，所述第五涂层包括氧化物电解质；所述负极集流体远离负极活性层的一侧设置有第六涂层，所述第六涂层包括氧化物电解质；
    所述第五涂层和第六涂层中，所述氧化物电解质的D50独立地为0.05μm～1.2μm；所述氧化物电解质独立地选自Li1.4Al0.4Ti1.6(PO4)3或Li7La3Zr2O12。
  20. 根据权利要求19所述的半固态锂电池，其特征在于，其最低保液系数为1.25～1.45g/Ah；其高温循环1000cls容量保持率为65％以上；其高温循环1000cls的膨胀率为14％以下；其-20℃容量保持率为55％以上；其-20℃拉载次数为45次以上；其2C/0.2C倍率放电容量为92％以上；其热箱温度为130℃以上。
  21. 终端，包括权利要求1～20任意一项所述的半固态锂电池。
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