WO2026020681A1 - Matériau d'électrode positive à haute tenbeur en nickel modifié, son procédé de préparation et son utilisation - Google Patents

Matériau d'électrode positive à haute tenbeur en nickel modifié, son procédé de préparation et son utilisation

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Publication number
WO2026020681A1
WO2026020681A1 PCT/CN2024/137650 CN2024137650W WO2026020681A1 WO 2026020681 A1 WO2026020681 A1 WO 2026020681A1 CN 2024137650 W CN2024137650 W CN 2024137650W WO 2026020681 A1 WO2026020681 A1 WO 2026020681A1
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WIPO (PCT)
Prior art keywords
additive
modified high
cathode material
nickel cathode
application
Prior art date
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Pending
Application number
PCT/CN2024/137650
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English (en)
Chinese (zh)
Inventor
杨成
刘瑞福
朱健
侯鑫宇
曾琼瑶
黎力
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Gold Shine Energy Material Co Ltd
Hunan Changyuan Lico New Energy Co Ltd
Minmetals New Energy Materials Hunan Co ltd
Original Assignee
Gold Shine Energy Material Co Ltd
Hunan Changyuan Lico New Energy Co Ltd
Minmetals New Energy Materials Hunan Co ltd
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Application filed by Gold Shine Energy Material Co Ltd, Hunan Changyuan Lico New Energy Co Ltd, Minmetals New Energy Materials Hunan Co ltd filed Critical Gold Shine Energy Material Co Ltd
Publication of WO2026020681A1 publication Critical patent/WO2026020681A1/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

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Classifications

    • 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
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/40—Complex oxides containing nickel and at least one other metal element
    • C01G53/42—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/40—Complex oxides containing nickel and at least one other metal element
    • C01G53/42—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2
    • C01G53/44—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2 containing manganese
    • 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
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • 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

  • This application relates to the field of new energy technology, and in particular to a modified high-nickel cathode material, its preparation method, and its application.
  • Layered metal oxide cathode materials have formed relatively systematic and mature systems based on different elemental and compositional ratios. Among them, nickel-cobalt-manganese or nickel-cobalt-aluminum material systems can be collectively referred to as ternary materials. When the molar amount of nickel in a layered metal oxide cathode material exceeds 80% of the molar amount of the transition metal, it is called a high-nickel material. High-nickel materials have advantages such as high capacity, high specific energy, stable performance, and low cost, making them an attractive choice in fields such as power batteries, and are currently widely used and under in-depth research as cathode materials.
  • cathode materials such as pursuing the ultimate usable compaction density and predicting and preventing failure mechanisms during use. Therefore, for high-nickel cathode materials, while solving the technical and cost challenges of material synthesis, it is also necessary to consider material processing performance, such as hygroscopicity and pressure resistance. Furthermore, it is crucial to improve the compatibility of material volume changes and the continued occurrence of side reactions during battery cycling, ensuring that these characteristics are recognized and even accepted.
  • the powder materials need to undergo a high-pressure compaction process during electrode fabrication and an expansion and contraction process involving continuous particle insertion and extraction during battery cycling. Therefore, improving the pressure resistance and material strength of high-nickel/ultra-high-nickel materials is crucial for their application and for the technological development of high-energy-density batteries.
  • This application aims to address at least one of the technical problems existing in the prior art. To this end, this application proposes a modified high-nickel cathode material, which can effectively improve the voltage resistance of the obtained high-nickel cathode material and significantly enhance its powder strength and structural stability.
  • This application also provides a method for preparing the above-mentioned modified high-nickel cathode material.
  • This application also provides applications of the aforementioned modified high-nickel cathode material.
  • a modified high-nickel cathode material comprising:
  • Interstitial material the interstitial material being present inside the pores; the interstitial material comprising a sintered material derived from additive B,
  • Additive B contains boron nitride and a calcium-containing compound.
  • the matrix material itself has a stable structure, which can improve its compressive strength to a certain extent.
  • boron nitride is a lubricating substance, which is beneficial for filling gaps in the matrix material and can also improve pressure resistance.
  • the Ca ions in the calcium-containing compound can adhere to polyanions ( SO4 ⁇ , residues from the preparation of the precursor), thereby increasing the bonding strength between the interstitial material and the matrix material, and further enhancing the mechanical strength of the obtained modified high-nickel cathode material.
  • the obtained modified high-nickel cathode material can significantly reduce its internal porosity and improve its mechanical properties such as pressure resistance and crack resistance. Ultimately, this significantly reduces the particle cracking ratio and crack width of the obtained modified high-nickel cathode material during long-cycle or high-rate electrochemical processes.
  • it can specifically be 0.80, 0.85, 0.90, 0.91, 0.92, 0.93, 0.94, or 0.95.
  • M in the matrix material, is a combination of Co and Mn.
  • the molar ratio of Co to Mn is 1.5-2.5:1. Specifically, it can be 1.6:1, 1.7:1, 1.8:1, 1.9:1, or approximately 2:1, etc.
  • the matrix material can be 0.01 ⁇ y ⁇ 0.20, preferably 0.02 ⁇ y ⁇ 0.20, more preferably 0.04 ⁇ y ⁇ 0.20, and even more preferably 0.045 ⁇ y ⁇ 0.20. Specifically, it can be about 0.02, 0.03, 0.04, 0.045, 0.05, 0.06, 0.07, 0.08, 0.09, 0.10, 0.11, 0.12, 0.13, 0.14, 0.15, 0.16, 0.17, 0.18, 0.19, or about 0.20.
  • the matrix material can be 0.002 ⁇ z ⁇ 0.02, preferably 0.005 ⁇ z ⁇ 0.018.
  • it can be about 0.005, 0.006, 0.007, 0.008, 0.009, 0.01, 0.015 or about 0.018.
  • M’ in the matrix material, includes at least two of Zr, Sr, Y, Nb, Ca, Ti, Sb, and W. There are no particular limitations as long as it can provide a certain doping effect.
  • M’ includes at least two of Zr, Sr, Y, Nb, Ti, Sb, and W. More specifically, M’ includes at least two or at least one of Zr, Sr, Y, Nb, and W.
  • M’ is selected from a combination of Zr, Sr, Y, and W, or a combination of Zr, Sr, Nb, and W.
  • the molar percentage of Zr is 50% to 60%. For example, it can be 54%, 55%, or 56%, or other extreme values.
  • the molar percentage of Sr is 10% to 20%. For example, it can be 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, or 19%, or other extreme values.
  • the molar percentage of Y or Nb is 5% to 10%. For example, it can be 6%, 7%, 8%, or 9%.
  • the molar percentage of W is 15% to 30%. For example, the specific percentages could be 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, or 30%.
  • the matrix material has a divergent structure.
  • the matrix material is composed of secondary particles formed by the arrangement and stacking of primary particles.
  • the calcium-containing compound includes at least one of calcium carbonate, calcium hydroxide, calcium phosphate, and calcium pyrophosphate.
  • the concentration of element B derived from additive B in the modified high-nickel cathode material is from 200 ppm to 5000 ppm, preferably from 250 ppm to 4800 ppm. Specifically, it can be about 300 ppm, 500 ppm, 700 ppm, 800 ppm, 900 ppm, 1000 ppm, 2000 ppm, 3000 ppm, 4000 ppm, 4500 ppm, 4700 ppm, 4800 ppm, or about 4900 ppm.
  • the boron nitride structure includes at least one of nanowires and nanosheets. Further, the average equivalent particle size of the boron nitride is 25 nm to 35 nm. Specifically, it can be about 30 nm.
  • the coating layer is wrapped around the surface of the modified high-nickel cathode material.
  • the additive C contains at least one of boric acid, aluminum oxide, aluminum hydroxide, cerium oxide, aluminum fluoride, cerium fluoride, magnesium oxide, and magnesium hydroxide.
  • the additive C comprises boric acid, and at least one selected from aluminum oxide, aluminum hydroxide, cerium oxide, aluminum fluoride, cerium fluoride, magnesium oxide, and magnesium hydroxide.
  • the additive C comprises boric acid, and at least one selected from cerium fluoride, magnesium oxide, and aluminum fluoride.
  • the mass ratio of boric acid to other substances in additive C is 0.025-5:1, preferably 0.1-4:1. For example, it can be 0.1:1, 0.2:1, 0.5:1, 1:1, 1.5:1, 2:1, 3:1, or 4:1, etc.
  • the modified high-nickel cathode material actually possesses a core-shell structure, wherein:
  • the core includes a matrix material and an interstitial material disposed within the pores of the matrix material;
  • the shell is a coating layer that surrounds the surface of the core and contains a sintered material derived from additive C.
  • the coating layer accounts for 0.1% to 4% of the mass percentage of the modified high-nickel cathode material, preferably 0.5% to 3.5%, and more preferably 0.5% to 2.0%. Specifically, it can be about 0.5%, 1.0%, 1.5%, 2.0%, 3.0%, or about 3.5%.
  • the collapse point P ⁇ of the modified high-nickel cathode material is 40 MPa to 65 MPa. This collapse point refers to the point at which the compaction density decreases under continuously varying pressure.
  • the breakdown point of the modified high-nickel cathode material provided in this application is increased by more than 10% compared to the breakdown point of existing high-nickel cathode materials with the same nickel content. In actual production, the improvement can reach 20%, or even 40% or about 80% or more.
  • the porosity of the modified high-nickel cathode material is ⁇ 3%.
  • porosity refers to the percentage of blank area to the total area of the particles in a cross-sectional SEM image. Typically, it is necessary to compile cross-sectional SEM images of multiple modified high-nickel cathode materials.
  • the porosity of the modified high-nickel cathode material is 0.1% to 3.0%, preferably 0.1% to 2.0%, more preferably 0.1% to 1.0%, further preferably 0.25% to 0.8%, and even more preferably 0.25% to 0.57%. Specifically, it can be about 0.1%, 0.15%, 0.2%, 0.25%, 0.28%, 0.3%, 0.31%, 0.32%, 0.33%, 0.35%, 0.4%, 0.5%, 0.6%, 0.55%, 1.0%, 1.1%, 1.2%, 1.3%, or about 1.5%.
  • the modified high-nickel cathode material has a divergent structure and a composite interstitial structure, that is, the primary particles are divergent from the inside out, with better regularity, improved uniformity of pore distribution between primary particles, generally smaller pores, and the pores are filled with a specific interstitial material.
  • the particle cross-section of the modified high-nickel cathode material was observed on the electrode sheet. The results showed that compared with conventional high-nickel cathode materials, the degree of cracking was improved, and the number and width of cracks were significantly reduced.
  • a method for preparing a modified high-nickel cathode material is provided.
  • the modified high-nickel cathode material in this preparation method can be the aforementioned modified high-nickel cathode material comprising a matrix material and an interstitial material.
  • the preparation method includes mixing a precursor Ni ⁇ sub>a ⁇ /sub> M ⁇ sub>b ⁇ /sub> (OH) ⁇ sub>2 ⁇ /sub>, a lithium source, additive A, and additive B in an aerobic environment and performing a single sintering to obtain a single-sintered product.
  • the primary sintering product contains a matrix material and an interstitial material. Transition metal elements such as Ni, Co, and Mn are derived from the precursor and additive A, M’ is derived from additive A, and the interstitial material is derived from additive B.
  • the additive A is at least two of the oxides, hydroxides or carbonates of Zr, Sr, Ca, Mg, Ba, Y, Nb, Ti, Mo, Sn, Ta, Sb, Bi and W;
  • Additive B contains boron nitride and a calcium-containing compound
  • the first sintering process includes a first heat preservation platform and a second heat preservation platform; the temperature of the first heat preservation platform is 350°C to 650°C; and the temperature of the second heat preservation platform is 680°C to 900°C.
  • additive A acts as a dopant
  • trace amounts of additive A not incorporated into the crystal lattice may exist in the gaps and surface of the modified high-nickel cathode material.
  • Additive B acts as a gap filler, and trace amounts of additive B may participate in initial doping and surface coating; trace amounts of sintered additive B may exist on the surface of the matrix material, but this does not affect performance.
  • the second holding platform facilitates crystal reshaping and growth, and effectively releases internal stress within the crystal.
  • the temperature limitation of the first insulation platform allows the lithium source and additive A to achieve optimal melting effect and reactivity, which is more conducive to the melting and infiltration of lithium salt and additive A into the gaps of the precursor. Furthermore, the element M' in additive A and Li in lithium salt penetrate into the primary particles and form part of the crystal lattice, resulting in a sintered material with modified grain morphology.
  • the first insulation platform can also significantly improve the temperature uniformity of the mixture to be sintered and achieve sufficient oxygen concentration in the microenvironment atmosphere by fully venting for a certain period of time.
  • the setting of the second insulation platform mainly takes into account the thermodynamic reaction conditions, and the constant temperature of this platform for a period of time is conducive to the full development of crystals and the release of surface stress, forming a material with complete crystal form and stable surface structure.
  • Lithium salts and precursors also act as fluxes, lowering the melting/decomposition temperature of additive B to some extent, causing it to decompose into smaller particles and fully perform its gap-filling function.
  • additive B itself acts as a sintering aid.
  • the Ca element in calcium-containing compounds can combine with anions such as S during sintering, improving lithium utilization. It can also lower reaction energy barriers and modify crystal surfaces and grain interfaces, further promoting the adhesion and bonding of the sintered product of additive B to the matrix material, enhancing the gap-filling effect.
  • additive B contains boron nitride
  • the N-B bonds in boron nitride are extremely strong, making the substance very stable with a melting point of around 3100 degrees Celsius, suitable for use as a lubricant and interface stabilizer.
  • the high melting/decomposition temperature of additive B combined with the high temperature of the second insulation platform, promotes its decomposition into smaller particle sizes, thus achieving the gap-filling effect.
  • the particle strength of the obtained modified high-nickel cathode material is unexpectedly and significantly improved, and its voltage resistance is ultimately improved.
  • the collapse point P ⁇ was obtained.
  • the results showed that the P ⁇ of the modified high-nickel cathode material prepared in this application was significantly improved compared with the traditional high-nickel cathode material.
  • the cracking of the modified high-nickel cathode material provided in this application was significantly improved by scanning electron microscopy.
  • the modified high-nickel cathode material prepared according to the method of the second aspect of this application can be obtained according to the first aspect of this application.
  • the value of a ranges from 0.8 to 0.956.
  • it can specifically be about 0.81, 0.85, 0.88, 0.9, 0.91, 0.92, 0.93 or about 0.95.
  • the value of b ranges from 0.02 to 0.2, preferably from 0.08 to 0.2.
  • it can specifically be about 0.02, 0.03 , 0.04, 0.045, 0.05, 0.06, 0.08, 0.1, 0.11, 0.12, 0.15, or about 0.2.
  • the porosity of the precursor is 2% to 15%, preferably 3% to 10%, more preferably 3% to 5%, specifically about 3%, 3.2%, 3.8%, 4%, 4.2%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, 8.5%, 9%, 9.5%, or about 10%.
  • the porosity of the precursor is greater than that of the modified high-nickel cathode material because, on the one hand, the porosity of the precursor decreases after primary sintering and secondary sintering, and on the other hand, the additive B has a gap-filling effect, ultimately significantly reducing the porosity.
  • the particle size D50 of the precursor is 2 ⁇ m to 20 ⁇ m, preferably 4 ⁇ m to 15 ⁇ m, more preferably 10 ⁇ m, 11 ⁇ m, 11.5 ⁇ m, 12 ⁇ m or about 12.5 ⁇ m.
  • the precursor is either self-made or commercially purchased. Whether self-made or commercially purchased, crystal growth can be carried out in stages, controlling the flow rate/solid content ratio of the mixed metal salt in different growth stages to allow rapid crystallization and growth within the system, ultimately yielding a high-porosity precursor with good sphericity, narrow distribution, and radial distribution from the inside out.
  • the high porosity of the precursor is beneficial during the mixing process of primary sintering, facilitating the melting and infiltration of additive A, and promoting the filling of additive B into the pores of the precursor.
  • the additive A includes at least two of oxides, hydroxides, or carbonates of Zr, Sr, Nb, and W.
  • determining the type and amount of additive A based on the chemical formula of the target matrix material is a routine operation.
  • the chemical composition of the matrix material can usually be calculated from the raw materials and their amounts.
  • the insulation time of the second insulation platform is 6 hours to 16 hours.
  • it can be approximately 10 hours, 12 hours, 14 hours, or 15 hours.
  • the first heat preservation platform is used first, followed by the second heat preservation platform. After the first sintering, the temperature is lowered to room temperature, which can be done naturally. After cooling, the material can be crushed.
  • the amount of additive B added should be determined appropriately based on various specific conditions such as the concentration or porosity of the modified high-nickel cathode material.
  • the preparation method further includes washing the product sintered in the first sintering with water, and mixing the washed product with additive C and then performing a second sintering.
  • the mass ratio of the water used to the mass of the product sintered in the first sintering is 0.4-2.0:1, preferably 0.5-1.5:1. Specifically, it can be about 0.5:1, 1:1, or about 1.5:1. This effectively removes residual alkali and improves the processing performance of the modified high-nickel cathode material.
  • the water washing temperature is 5°C to 30°C, preferably 10°C to 25°C. Specifically, it can be about 10°C, 15°C, 20°C, or about 25°C, or it can be an extreme value, as mentioned above. In actual production, the temperature can be selected and adjusted as needed; this application does not impose strict limitations.
  • the water washing time is from 3 minutes to 50 minutes, preferably from 5 minutes to 45 minutes. Specifically, it can be about 5 minutes, 10 minutes, 15 minutes, 20 minutes, 25 minutes, 30 minutes, 40 minutes, or about 45 minutes.
  • the water washing time refers to the time from when the product obtained from the first sintering is completely wetted by water until solid-liquid separation is complete.
  • the solid-liquid separation method includes at least one of filtration and centrifugation.
  • the preparation method further includes drying the water-washed product obtained after the water washing.
  • the drying temperature is 100°C to 160°C. Specifically, it can be about 100°C, 110°C, 120°C, 130°C, 140°C, 150°C, or about 160°C, preferably 100°C to 130°C.
  • the isothermal temperature for the secondary sintering is 200°C to 400°C, preferably 250°C to 350°C.
  • it can be approximately 250°C, 300°C, or approximately 350°C.
  • the duration of the secondary sintering is 5 to 10 hours, preferably 6 to 8 hours.
  • the preparation method includes the following steps:
  • NiaMb (OH) 2 the precursor NiaMb (OH) 2 , lithium source, additive A and additive B are mixed and sintered once.
  • step S2 The product obtained in step S2 is mixed with additive C and then subjected to secondary sintering.
  • a lithium secondary battery wherein the raw materials for preparing the lithium secondary battery include the modified high-nickel cathode material described above, or the modified high-nickel cathode material prepared by the preparation method described above.
  • the lithium secondary battery adopts all the technical solutions of the modified high-nickel cathode material described in the above embodiments, it possesses at least all the beneficial effects brought about by the technical solutions of the above embodiments. That is, the lithium secondary battery has excellent volumetric energy density and excellent cycle performance.
  • the lithium secondary battery includes at least one of button cells, pouch cells, prismatic cells, and cylindrical cells.
  • the capacity retention rate of the lithium secondary battery after 50 cycles at 1C is ⁇ 91%. Specifically, it can be 91%, 92%, 93%, 94%, 95%, 96%, or approximately 97%.
  • Figure 1 is a cross-sectional SEM image of the modified high-nickel cathode material obtained in Example 1 of this application.
  • Figure 3 is a diagram showing the withstand voltage performance of the modified high-nickel cathode materials obtained in Example 1 and Comparative Example 1 of this application.
  • Figure 4 is a cross-sectional SEM image of the modified high-nickel cathode material obtained in Example 1 of this application after cycling.
  • Figure 5 is a cross-sectional SEM image of the modified high-nickel cathode material obtained in Comparative Example 1 of this application after cycling.
  • Figure 6 is a cycle performance diagram of Embodiment 1 and Comparative Example 1 of this application.
  • Figure 7 shows the EDS spectra of the high-nickel cathode materials obtained in Examples 1 (a-b) and Comparative Examples 1 (c-d) of this application.
  • Figure 8 is a surface SEM image of the modified high-nickel cathode material obtained in Example 1 of this application.
  • Figure 9 is a surface SEM image of the high-nickel cathode material obtained in Comparative Example 1 of this application.
  • the terms “one embodiment,” “some embodiments,” “illustrative embodiment,” “example,” “specific example,” or “some examples,” etc. refer to specific features, structures, materials, or characteristics described in connection with that embodiment or example, which are included in at least one embodiment or example of this application.
  • the illustrative expressions of the above terms do not necessarily refer to the same embodiment or example.
  • the specific features, structures, materials, or characteristics described may be combined in any suitable manner in one or more embodiments or examples.
  • the transition metal elements Ni, Co, and Mn come from the precursor, the dopant element M' comes from additive A, and the interstitial material comes from additive B;
  • NiaMb (OH) 2 has the chemical formula Ni 0.918 Co 0.051 Mn 0.031 (OH) 2 ; the D50 particle size is approximately 11.5 ⁇ m; and the porosity is approximately 3.8%.
  • the molar ratio of lithium to precursor in the lithium salt is 1.03:1;
  • Additive A is a mixture of zirconium oxide, strontium oxide, yttrium oxide, and tungsten trioxide, with the mixing ratio calculated based on the composition of M';
  • Additive B is a mixture of boron nitride (flakes, with an average equivalent particle size of about 30 nm) and calcium hydroxide. The amount added is calculated based on the concentrations of element B and element Ca in the product obtained in this step as shown in Table 1.
  • the sintering process includes a first holding platform and a second holding platform, which are carried out sequentially.
  • the temperature is increased to the first holding platform at 2°C per minute and then held at that temperature.
  • the temperature is then increased to the second holding platform at 2°C per minute and held at that temperature again.
  • the constant temperature of the first holding platform is 450°C and the holding time is 3 hours.
  • the constant temperature of the second holding platform is 750°C and the holding time is 12 hours.
  • the primary sintering product obtained in step S1 is washed with pure water, wherein the mass ratio of pure water to primary sintering product is 1:1, the washing temperature is 15°C, and the washing time is 20min; then it is dried at 120°C.
  • step S2 The product obtained in step S2 was mixed with additive C and subjected to secondary sintering at 310°C for 7 hours. The mixture was then passed through a 325-mesh sieve to obtain the modified high-nickel cathode material of this application; the porosity is shown in Table 2.
  • additive C includes boric acid and cerium fluoride, with a mass ratio of boric acid to cerium fluoride of 3:1, and the amount added is 1.5% of the mass percentage of the primary sintering product.
  • the precursor NiaMb (OH) 2 has the chemical formula Ni0.802Co0.12Mn0.078 (OH) 2 ; the D50 particle size is approximately 12.5 ⁇ m ; and the porosity is approximately 3.2%.
  • the molar ratio of lithium to precursor in the lithium salt is 1.04:1;
  • Additive A is a mixture of zirconium oxide, strontium oxide, yttrium oxide and tungsten trioxide, and the mixing ratio is calculated according to the composition of M’;
  • Additive B is a mixture of boron nitride (flakes, with an average equivalent particle size of about 30 nm) and calcium hydroxide. The amount added is calculated based on the concentrations of element B and element Ca in the product obtained in this step as shown in Table 1.
  • a single sintering process includes a first holding platform and a second holding platform, which are carried out sequentially.
  • the temperature is increased to the first holding platform at 2°C per minute and then held at that temperature.
  • the temperature is then increased to the second holding platform at 2°C per minute and held at that temperature again.
  • the constant temperature of the first holding platform is 600°C and the holding time is 2 hours.
  • the constant temperature of the second holding platform is 830°C and the holding time is 6 hours.
  • the primary sintering product obtained in step S1 is washed with pure water, wherein the mass ratio of pure water to primary sintering product is 1.5:1, the washing temperature is 25°C, and the washing time is 15min; then it is dried at 130°C.
  • step S2 The product obtained in step S2 was mixed with additive C and subjected to secondary sintering at 350°C for 6 hours. The mixture was then passed through a 325-mesh sieve to obtain the modified high-nickel cathode material of this application.
  • additive C includes boric acid and cerium fluoride, with a mass ratio of boric acid to cerium fluoride of 0.5:1, and the amount added is 0.5% of the mass percentage of the primary sintering product.
  • the primary sintering product contains matrix material and interstitial material
  • the transition metal elements Ni, Co, and Mn come from the precursor, the dopant element M' comes from additive A, and the interstitial material comes from additive B.
  • the precursor NiaMb (OH) 2 has the chemical formula Ni0.956Co0.029Mn0.015 ( OH) 2 ; the D50 particle size is approximately 11.0 ⁇ m ; and the porosity is approximately 4.2%.
  • the molar ratio of lithium to precursor in the lithium salt is 1.02:1;
  • Additive A is a mixture of zirconium oxide, strontium oxide, niobium oxide and tungsten trioxide, and the mixing ratio is calculated according to the composition of M’;
  • Additive B is a mixture of boron nitride (flakes, with an average equivalent particle size of about 30 nm) and calcium hydroxide. The amount added is calculated based on the concentrations of element B and element Ca in the product obtained in this step as shown in Table 1.
  • the sintering process includes a first holding platform and a second holding platform, which are carried out sequentially.
  • the temperature is increased to the first holding platform at 2°C per minute and then held at that temperature.
  • the temperature is then increased to the second holding platform at 2°C per minute and held at that temperature again.
  • the constant temperature of the first holding platform is 480°C and the holding time is 6 hours.
  • the constant temperature of the second holding platform is 710°C and the holding time is 15 hours.
  • the primary sintering product obtained in step S1 is washed with pure water, wherein the mass ratio of pure water to primary sintering product is 0.5:1, the washing temperature is 10°C, and the washing time is 30min; then it is dried at 100°C.
  • step S2 The product obtained in step S2 was mixed with additive C and subjected to secondary sintering at 250°C for 8 hours. The mixture was then passed through a 325-mesh sieve to obtain the modified high-nickel cathode material of this application.
  • additive C includes boric acid and cerium fluoride, with a mass ratio of boric acid to cerium fluoride of 4:1, and the amount added is 2.0% of the mass percentage of the primary sintering product.
  • step S3 cerium fluoride in additive C is replaced with magnesium oxide. Otherwise, the raw materials, preparation methods, and parameter conditions are basically the same as in Example 1.
  • step S3 cerium fluoride in additive C is replaced with aluminum fluoride. Otherwise, the raw materials, preparation methods, and parameter conditions are basically the same as in Example 1.
  • step S1 calcium hydroxide Ca(OH) 2 in additive B is replaced with calcium pyrophosphate Ca2O7P2 . Otherwise, the raw materials, preparation methods and parameters are basically the same as in Example 1.
  • step S2 Based on Example 1, after drying in step S2, the material is directly crushed and passed through a 325-mesh sieve to obtain the modified high-nickel cathode material of this application. That is, there is no mixing and secondary sintering in step S3. Apart from this, the raw materials, preparation methods and parameter conditions are basically the same as in Example 1.
  • Table 1 below shows some parameters for Examples 1 to 7.
  • step S1 additive B does not contain boron nitride.
  • step S1 additive B does not contain calcium hydroxide.
  • step S1 the first insulation platform is not set up, that is, the temperature is directly raised from room temperature to the constant temperature of 780°C of the second insulation platform and kept at that temperature for 12 hours.
  • step S1 the temperature of the first insulation platform is set to 700°C.
  • step S1 the insulation temperature of the first insulation platform is 300°C.
  • step S1 no additive A is added.
  • This example provides a lithium secondary battery, as detailed below:
  • the battery is assembled in the following order: 16 ⁇ m thick electrolyte, 8 drops of electrolyte, positive electrode plate, and positive electrode shell.
  • the battery shell (positive and negative electrode shells) is 24mm in size.
  • the assembled coin cell is placed in the mold of a hydraulic sealing machine (purchased from Shenzhen Kejing Zhida Technology Co., Ltd.), locked, and pressure >450kg/ cm2 is applied. Then, it is unlocked, and the sealed coin cell is removed, which is the lithium secondary battery obtained in this example.
  • a hydraulic sealing machine purchased from Shenzhen Kejing Zhida Technology Co., Ltd.
  • This example tests the cross-sectional morphology of the modified high-nickel cathode materials obtained in the examples and comparative examples.
  • the test method is to perform SEM testing after cross-section.
  • the cross-sectional SEM images of Example 1 and Comparative Example 1 are shown in Figures 1 and 2.
  • the test results show that the cross-sectional morphology of the modified high-nickel cathode materials obtained in the examples of this application is similar, both having radially arranged primary particles, which aggregate to form a secondary spherical structure; the gaps between the primary particles are filled with pore fillers derived from additive B. From the appearance, the cross-section of the modified high-nickel cathode material obtained in Example 1 is denser. In contrast, Comparative Example 1 lacks pore fillers, and the cross-section shows significantly more pores.
  • FIG. 7 is a cross-sectional SEM image of the cathode material obtained in Example 1
  • (b) is a mapping image of the B element distribution in the cross-section of the cathode material obtained in Example 1, where white dots represent B element, which is uniformly distributed in the internal and external layers.
  • (c) is a cross-sectional SEM image of the cathode material obtained in Comparative Example 1
  • (d) is a mapping image of the B element distribution in the cross-section of the cathode material obtained in Comparative Example 1, where white dots represent B element, which is faintly visible in the external layer.
  • the boron element from additive C is mainly enriched on the surface of the material; according to the cross-sectional EDS spectrum of Example 1, the modified high-nickel cathode material of Example 1 also has relatively abundant boron element in its interior, including the core. Therefore, it can be concluded that the sintered material containing boron element from additive B does indeed have an interstitial filling effect.
  • This example also tested the withstand voltage performance of the modified high-nickel cathode materials obtained in the examples and comparative examples.
  • the specific test method was as follows: gradually pressurize the cathode materials obtained in the examples and comparative examples to obtain the abrupt change point of d ⁇ /dP.
  • the pressure applied at the corresponding position is the collapse point; where ⁇ is the density and P is the pressure applied during the process; the test results are shown in Figure 3 and Table 2; the position indicated by the arrow in Figure 3 is the collapse point.
  • Example 1 and Comparative Example 1 are shown in Figures 1-2 and Figures 8-9, respectively. They all show that the porosity of Example 1 is lower than that of Comparative Example 1.
  • the porosity statistics are shown in Table 2.
  • This example also tested the cycle performance of the lithium-ion secondary battery obtained from the application example. After cycling, the battery was disassembled, and the cross-sectional structure of the high-nickel cathode material after cycling was captured by SEM.
  • the test method for cycle performance is as follows:
  • Cycle capacity retention (%) (50th cycle discharge capacity / 1st cycle discharge capacity) ⁇ 100%.
  • Example 1 The cyclic process of Example 1 and Comparative Example 1 shows that, compared with Example 1, Comparative Example 1 decays faster in the first 50 weeks and has a faster overall decay rate, as shown in Figure 6.
  • Figures 4 and 5 show a comparison of the cross-sectional morphology of the high-nickel cathode materials after cycling in Example 1 and Comparative Example 1. Based on the cross-sectional test results of the cycled high-nickel cathode materials, the number and width of cracks in the modified high-nickel cathode materials obtained in the examples are significantly reduced. This demonstrates that the modified high-nickel cathode material provided in this application can significantly improve the stability of the cycling structure and ultimately significantly improve cycling performance.
  • this application by leveraging the synergistic effects of additives A and B, and preferably by leveraging the synergistic effects of additives A, B, and C, and by precisely controlling the process parameters in each step of S1, such as the sintering regime and sintering temperature, unexpectedly obtained a modified high-nickel cathode material with excellent pressure resistance and cycle stability.
  • the cycle performance of the lithium secondary batteries can be significantly improved.
  • lithium secondary batteries are expected to find wide application in the fields of power batteries, energy storage technology, and 3C small household appliance technology.

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Abstract

La présente demande se rapporte au domaine technique de la nouvelle énergie, et divulgue un matériau d'électrode positive à haute teneur en nickel modifié, son procédé de préparation et son utilisation. Le matériau d'électrode positive à haute teneur en nickel modifié fourni par la présente demande comprend un matériau de matrice poreux ayant une formule chimique générale LiNixMyM'zO2, et une substance de charge interstitielle, où 0,80 ≤ x ≤ 0,98, 0 < y ≤ 0,20, 0 < z ≤ 0,02, x + y + z = 1, M est au moins deux parmi Co, Mn et Al, et M' est au moins deux parmi Zr, Sr, Ca, Mg, Ba, Y, Nb, Ti, Mo, Sn, Ta, Sb, Bi et W. La substance de charge interstitielle est située à l'intérieur de pores dans le matériau de matrice et comprend un fritté dérivé d'un additif B, et l'additif B comprend du nitrure de bore et un composé contenant du calcium. Le matériau d'électrode positive à haute teneur en nickel modifié selon la présente demande présente une excellente résistance à la pression et une excellente stabilité de structure en cycle. La présente demande concerne en outre un procédé de préparation et une utilisation du matériau d'électrode positive à haute teneur en nickel modifié.
PCT/CN2024/137650 2024-07-25 2024-12-06 Matériau d'électrode positive à haute tenbeur en nickel modifié, son procédé de préparation et son utilisation Pending WO2026020681A1 (fr)

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