WO2023151334A1 - High-energy-density positive electrode material, positive electrode sheet and lithium-ion battery - Google Patents

High-energy-density positive electrode material, positive electrode sheet and lithium-ion battery Download PDF

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Publication number
WO2023151334A1
WO2023151334A1 PCT/CN2022/132003 CN2022132003W WO2023151334A1 WO 2023151334 A1 WO2023151334 A1 WO 2023151334A1 CN 2022132003 W CN2022132003 W CN 2022132003W WO 2023151334 A1 WO2023151334 A1 WO 2023151334A1
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positive electrode
lithium
additive
lfp
positive
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PCT/CN2022/132003
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French (fr)
Chinese (zh)
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刘晓蕾
陈蓓娜
闫晟睿
高天一
胡景博
高华文
姜涛
荣常如
孙焕丽
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中国第一汽车股份有限公司
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Publication of WO2023151334A1 publication Critical patent/WO2023151334A1/en

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—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
    • 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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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 invention belongs to the technical field of lithium-ion batteries, and in particular relates to a high-energy-density positive electrode material, a positive electrode sheet and a lithium-ion battery.
  • lithium-ion batteries are used in cascade utilization of logistics vehicles, buildings, and base stations after being retired from vehicles. It is necessary to further improve the service life of lithium-ion batteries.
  • the negative electrode active material of lithium-ion batteries is mainly graphite negative electrode
  • the lithium intercalation potential of graphite negative electrode is lower than the reduction potential of organic electrolytes, such as PC, EC, and DEC. Therefore, during the first charging process, the electrolyte will be reduced to form a solid electrolyte film (SEI) on the surface of the negative electrode.
  • SEI solid electrolyte film
  • This process not only involves electrons, but also lithium ions.
  • lithium-containing organic substances such as LiF, Li 2 CO 3 , such as alkyl lithium carbonate, are generated.
  • the graphite negative electrode does not contain lithium in lithium-ion batteries
  • the positive electrode as the only source of lithium in the formation of SEI, will cause a loss of 7%-15% of active lithium, which will affect the energy density and service life of the power battery.
  • lithium supplementation through slurry that is, metal lithium or lithium-containing organic matter, modified materials, etc., negative electrode materials and non-aqueous liquids are mixed to form a slurry, the slurry is coated on the current collector, and then dried, rolled, injected, etc. Liquid and other processes.
  • metal lithium has high reactivity and is very easy to react with oxygen and moisture in the air. Therefore, the requirements for moisture control in the preparation process are also extremely strict, thereby increasing the difficulty of the process.
  • lithium-ion batteries have extremely high requirements on the purity of various materials, once impurities are introduced into the lithium-containing materials used, it will have a negative impact on battery performance. Or through surface-treated stable metal lithium powder, but limited by its high activity, it is difficult to use the operating time of the lithium-ion battery process. At the same time, lithium powder is easy to float in the air, posing a great safety hazard. Or use lithium-rich lithium salts, lithium oxides, lithium-containing organic materials and other materials to supplement lithium at the material level at the positive electrode. difficulty.
  • the prior art discloses a method and system for replenishing lithium on a pole piece.
  • a base material to a metal lithium sheet or a lithium strip
  • the strength of the lithium strip is enhanced
  • a lithium strip is formed between the lithium strip and the composite device. Barrier, so that the lithium ribbon will not be in direct contact with the composite device during the transportation process, thus avoiding the lithium ribbon being torn or pinched during the production process.
  • this method has extremely high environmental requirements in the manufacturing process to avoid the reaction of metal lithium with air and water, so it is difficult to apply in practice.
  • the prior art also discloses negative electrode lithium supplement slurry, negative electrode and lithium secondary battery.
  • Lithium supplement slurry is prepared by using metal lithium powder and prepolymer, and coated on the prepared negative electrode sheet, and then used light or Heating and other conditions cause the prepolymer in the lithium-replenishing slurry to undergo a polymerization reaction to form a macromolecular polymer, and then perform cold pressing to obtain a lithium-replenishing negative electrode sheet.
  • this method increases the complexity of making lithium-ion batteries, and it is difficult to maintain the uniformity of the lithium-supplementing slurry of metal lithium powder and prepolymer and the dispersion in the mass production process, and it is prone to sedimentation, resulting in The battery cell consistency is reduced.
  • the prior art also discloses a method of replenishing lithium to the positive electrode sheet of a lithium-ion battery.
  • the "wet method lithium replenishment” is realized, thereby effectively avoiding the dry method.
  • the metal lithium powder floats in the air during lithium supplementation to ensure production safety, and the whole process is simple and the cost is low.
  • the amount of lithium supplementation can be adjusted by the amount of organic lithium solution sprayed or dripped, and the time of spraying or dripping Accurate control to achieve the purpose of uniform lithium supplementation, prevent lithium deposition and deformation of the positive plate, improve the first-time efficiency of the battery, and then increase the energy density of the battery.
  • this method of lithium supplementation must be implemented in an inert atmosphere to ensure the stability of the highly active organic lithium solution, so it is difficult to apply in practice.
  • the purpose of the present invention is to address the deficiencies of the above-mentioned prior art, to provide a high energy density positive electrode material, and to provide a positive electrode sheet and a lithium-ion battery, mainly to solve the problem of low efficiency of the existing lithium-replenishing methods of lithium-ion batteries. It is complex and has certain security risks.
  • the positive electrode material contains positive electrode active materials and additives
  • the LFP-X shell material is a pure-phase LiFePO4 material or a pure-phase LiFePO4 metal-doped LFP-X material, wherein X can be metals such as Mg, Mn, Al, Ti, V, Nb, Sb, etc.
  • the Li 2 NixMyO 2 @LFP-X material is made by chemical or physical methods, and the particle size of the Li 2 NixMyO 2 @LFP-X material is 1-10um, wherein Li 2 NixMyO 2
  • the particle size of the core material is 0.5-9.5um, and the particle size of the LFP-X shell material is 0.5-5um.
  • the chemical method is a solid-phase method or a liquid-phase method
  • the solid-phase method is selected from high-temperature solid-phase reaction method, carbothermal reduction method, microwave synthesis and pulsed laser deposition synthesis, sol-gel method, water Thermal synthesis method, precipitation method and solvothermal synthesis method
  • the physical method is selected from high-energy ball milling and physical vapor deposition method.
  • the Li 2 Ni x My O 2 @LFP-X material is selected as Li 2 CO 3 , LiOH, Li 2 O, CH 3 COOLi, LiNO 3 and Li 2 C 2 O lithium sources during the preparation process.
  • the iron source is one or more of Fe 2 O 3 , FeOOH, Fe(OH) 3 , Fe(NO3) 3 , Fe 2 (SO4) 3
  • the nickel source is NiO, One or more of NiO 2 , NiOOH, Ni(OH) 2 , NiNO 3 , Ni 2 SO 4 , metal source, that is, M is Cu, Al, Fe, Mn, Co, Ti, Sb, Mg and other metal elements
  • MOx, MO(OH)x, M(NO 3 )x, M(SO 4 )x where x depends on the valence state of the metal element.
  • a positive electrode sheet including a metal current collector and a high energy density positive electrode material
  • the additive is directly coated on the metal current collector together with the positive electrode active material, or the additive with a thickness of micron is sprayed on the electrode sheet with the positive electrode active material.
  • the mass percentage of the additive and the positive electrode active material is a, 0% ⁇ a ⁇ 50%.
  • the mass percentage of the additive and the positive electrode active material is 5%-15%.
  • the additive is prepared into a slurry, it is coated on the surface of the positive electrode active material sheet by spraying, screen printing, or doctor blade, with a thickness of 1-10 um.
  • a lithium-ion battery the lithium-ion battery includes a battery case, a pole core and an electrolyte, the pole core and the electrolyte are sealed in the battery case, the pole core includes a positive pole, a negative pole, and a battery between the positive pole and the negative pole
  • the separator the positive electrode includes a positive electrode current collector and a high energy density positive electrode material on the positive electrode current collector.
  • the present invention provides a high-energy-density positive electrode material, a pole piece and a lithium-ion battery.
  • the present invention uses a specific type of additive in the positive electrode material as a core-shell material of Li 2 Ni x My O 2 @LFP-X, Among them, Li 2 Ni x My O 2 has extremely high theoretical specific capacity and actual specific capacity, which can reach 300-600mAh/g;
  • the remaining reversible capacity of the additive material enables it to act as a positive electrode active material during battery use, which improves the energy density and life of the power battery;
  • the additive can be processed in the same way as the general positive active material in the production process of lithium-ion batteries. It can be directly coated on the positive electrode metal current collector together with the positive electrode active material, or sprayed on the electrode sheet with the positive electrode active material to make a high energy density positive electrode sheet without additional manufacturing processes or Environmental control is easier to implement in actual production and avoids the safety hazards of general lithium supplementation technology.
  • Figure 1 is a schematic diagram of the core-shell material of Li 2 Ni x M y O 2 @LFP-X;
  • Figure 2 is a schematic diagram of a high energy density positive pole piece
  • Figure 3 Lithium-ion battery charge and discharge curve for the first time.
  • the present invention provides a high-energy-density positive electrode material.
  • the positive electrode material contains positive electrode active materials and additives, and the additive is a core-shell material of Li 2 NixMyO 2 @LFP-X, that is, in Li 2
  • the Ni x M y O 2 material is physically or chemically coated with a layer of LFP-X material.
  • M is Cu, Al, Fe, Mn, Co, Ti, Sb, Mg and other metal elements, or B, F and other non-metallic elements, in order to achieve its specific capacity up to It can reach 300-600mAh/g, or even higher.
  • the remaining reversible capacity of the additive enables it to act as a positive electrode active material during battery use, so as to improve the energy density and prolong the service life of the power battery.
  • the additive is physically or chemically coated with a layer of LFP-X material on the outside of the Li 2 Ni x My O 2 material, which ensures the stability of the additive in the air, and can be compared with general positive active materials during storage or manufacturing.
  • the processing method is the same.
  • the LFP-X shell material can be a pure phase LiFePO4 material, or a pure phase LiFePO4 metal-doped LFP-X material, wherein X can be Mg, Mn, Al, Ti, V, Nb, Sb and other metals , to improve the electrical conductivity inside the pure-phase LiFePO4 crystal.
  • the Li 2 Ni x M y O 2 @LFP-X material can be synthesized by chemical methods, such as solid-phase method, that is, high-temperature solid-phase reaction method, carbothermal reduction method, microwave synthesis and pulsed laser deposition method; or liquid Phase methods, such as sol-gel method, hydrothermal synthesis method, precipitation method and solvothermal synthesis method. Physical methods can also be used, such as high energy ball milling, physical vapor deposition and other methods.
  • the particle size of the Li 2 NixMyO 2 @LFP-X material is 1-10um, of which the particle size of the core material of Li 2 NixMyO 2 is 0.5-9.5um, and the particle size of the LFP-X shell material is 0.5-5um.
  • the Li 2 Ni x M y O 2 @LFP-X material can be selected as a lithium source in the preparation process of Li 2 CO 3 , LiOH, Li 2 O, CH 3 COOLi, LiNO 3 and Li 2 C 2 O 4 one or more of.
  • the iron source selected in the preparation process of the L Li 2 Ni x M y O 2 @LFP-X material can be Fe 2 O 3 , FeOOH, Fe(OH) 3 , Fe(NO3) 3 , Fe 2 (SO4) One or more of 3 .
  • the nickel source selected in the preparation process of the Li 2 Ni x My O 2 @LFP-X material can be one of NiO, NiO 2 , NiOOH, Ni(OH) 2 , NiNO 3 , Ni 2 SO 4 or Various.
  • MOx can be used One or more of , MO(OH)x, M(NO 3 )x, M(SO 4 )x, where x depends on the valence state of the metal element.
  • the additive is prepared together with the positive electrode active material and coated on the positive electrode metal current collector, wherein the mass percentage of the additive and the positive electrode active material is a, 0% ⁇ a ⁇ 50%, preferably 5%-15%,
  • the above slurry preparation and coating process are the same as the known general technology in the industry, and there is no need for additional environmental control and process procedures, as shown in Figure 2.
  • the additive material is prepared into a slurry using a known general technology in the industry, and is coated on the surface of the positive electrode active material electrode sheet by spraying, screen printing, or scraping, with a thickness of 1-10 um, as shown in Figure 2.
  • the invention provides a high-energy-density positive pole piece, the pole piece includes a metal current collector and a positive electrode material, the additive can be directly coated on the metal current collector together with the positive active material, or sprayed on the pole piece with the positive active material Additive materials with a thickness of 1-10um at the micron level.
  • the additive has high stability, and its particle size and surface energy are similar to those of general positive electrode materials. It can be directly prepared with the positive electrode active material and coated on the positive electrode metal current collector without additional manufacturing process or environmental control. , which is easier to realize in actual production, and at the same time avoids the safety hazards of general lithium supplementation technology.
  • the additive can be made into a lithium-supplementing slurry separately, and the additive material with a micron-level thickness can be sprayed and transferred on the pole piece with the positive active material, and the thickness can be 1-10um.
  • the A more stable protective layer is formed on the surface of the positive electrode active material to improve the safety of lithium-ion batteries under abuse conditions.
  • the separate additive slurry ensures the consistency of additive distribution on the pole piece.
  • the high energy density positive electrode material and positive electrode sheet of the present invention can be used to prepare lithium-ion batteries, and the positive electrode material is lithium iron phosphate, lithium cobaltate, lithium manganate, lithium nickelate, lithium-rich manganese base, nickel-cobalt-manganese Ternary, nickel-cobalt-aluminum ternary type, the negative electrode material is graphite, metal lithium, alloy type. At the same time, it can be used for lithium-ion batteries of different packaging types, including hard-shell square, soft-pack and cylindrical.
  • the invention provides a lithium-ion battery
  • the lithium-ion battery includes a battery case, a pole core and an electrolyte, the pole core and the electrolyte are sealed in the battery case
  • the pole core includes a positive pole, a negative pole, and a A separator between negative electrodes
  • the positive electrode includes a positive electrode collector and a positive electrode material on the positive electrode collector, and the positive electrode material is the positive electrode material provided by the present invention.
  • the lithium-ion battery adopts the positive electrode material provided by the present invention, that is, contains positive electrode active material and additive material, and is calculated by matching with the design of the negative electrode.
  • the mass percentage of the additive and the positive electrode active material is a, and generally 0% ⁇ a ⁇ 50 %, preferably 5%-15%.
  • the additive has no requirement on the type of positive electrode material, such as LFP, NCM, LMO, LTO, etc. commonly used in the industry, and has a wide range of applications.
  • the additive has no requirement on the type of negative electrode material, such as Gr, LTO, Gr-nano Si, Gr- SiOx , etc. commonly used in the industry, and has a wide range of applications.
  • the additive has no requirement on the type of diaphragm material, such as PP, PE, ceramic coating, PVDF coating modified diaphragm, etc. commonly used in the industry, and has a wide range of applications.
  • the additives have no requirements on the type of electrolyte materials, such as LiPF6, LiBOB, LiFSI electrolytes commonly used in the industry, and EC, DEC, DMC organic solutions, etc., and have a wide range of applications.
  • the high energy density cathode material, pole piece and lithium ion battery of the present application have at least the following improvements:
  • the content of additives is significantly increased, which greatly improves the efficiency of lithium supplementation, and at the same time greatly improves the energy density and life of lithium-ion batteries.
  • the stability of the lithium supplement additive material is significantly improved. Compared with the raw materials containing metal lithium strips and lithium powder, it avoids the problem of potential safety hazards.
  • Li 2 NiO 2 material can be obtained, and then in an argon-protected environment, mix it with a nano-LFP material with a mass percentage of 2%-5% for 5-20h using a high-energy ball mill to make the nano-LFP material on Li 2 NiO 2 A uniform coating is formed to obtain Li 2 NiO 2 @LFP material.
  • Li 2 CO 3 and FePO 4 with a molar ratio of 1-1.05:1 as raw materials, glucose ratio 16%, add 0.5-2% Mg 2 (OH) 2 CO 3 , use ethanol as dispersant, and mix by ball milling 6-10h, after vacuum drying at 80-100°C, sintering, the sintering temperature is 700-800°C, and the sintering time is 8-12h, the shell material of LFP-Mg can be obtained, and then the mass percentage is 95%
  • the -98% Li 2 Ni 0.5 Cu 0.5 O 2 material is mixed with a high-energy ball mill for 5-20 hours to obtain the Li 2 Ni 0.5 Cu 0.5 O 2 @LFP-Mg material.
  • Example 3 To prepare a lithium-ion battery, use the high-energy positive electrode material pole piece, graphite negative electrode, and separator in Example 3 to prepare and wind up to prepare a bare cell, then put the bare cell into the shell, inject liquid, and then place the battery in an environment of 25°C After standing still, the formation, shaping and degassing processes are carried out after the electrolyte is infiltrated, and finally a lithium-ion battery with high energy density is obtained, and its first efficiency can be found to be >99% in the formation test stage, as shown in Figure 3.
  • the lithium-ion battery containing Li2NiO2@LFP additive has a first-time efficiency of >99%.

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Abstract

The present invention provides a high-energy-density positive electrode material, a positive electrode plate and a lithium-ion battery. The positive electrode material comprises a positive electrode active substance and an additive. The positive electrode sheet comprises a metal current collector and a positive electrode material. The additive is directly coated on the metal current collector together with the positive electrode active substance, or an additive with a micron-level thickness is sprayed on the electrode sheet having the positive electrode active substance. The lithium-ion battery comprises a battery case, an electrode core and an electrolyte. The electrode core and the electrolyte are sealed in the battery case. The electrode core comprises a positive electrode, a negative electrode and a separator between the positive electrode and the negative electrode. The positive electrode comprises a positive electrode current collector and a high-energy-density positive electrode material on the positive electrode current collector. According to the present invention, a specific type of additive is used in the positive electrode material and has extremely high theoretical specific capacity and actual specific capacity. Active lithium with irreversible capacity can be used to supplement lithium consumed by a negative electrode SEI layer, thereby improving the energy density of the power battery and extending the service life of the power battery. The potential safety hazards of an ordinary lithium supplementing technology are avoided.

Description

一种高能量密度正极材料、正极极片和锂离子电池A kind of high energy density cathode material, cathode pole piece and lithium ion battery 技术领域technical field
本发明属于锂离子电池技术领域，具体涉及一种高能量密度正极材料、正极极片和锂离子电池。The invention belongs to the technical field of lithium-ion batteries, and in particular relates to a high-energy-density positive electrode material, a positive electrode sheet and a lithium-ion battery.
背景技术Background technique
近年来新能源市场不断发展成熟，随着整车续航要求的提升，高能量密度的锂离子电池需求量显著增加。同时，新能源车使用场景越加丰富，例如从车上退役后锂离子电池用于物流车、楼宇、基站的梯级利用，需要进一步提升锂离子电池的使用寿命。In recent years, the new energy market has continued to develop and mature. With the improvement of vehicle battery life requirements, the demand for lithium-ion batteries with high energy density has increased significantly. At the same time, the use scenarios of new energy vehicles are becoming more and more abundant. For example, lithium-ion batteries are used in cascade utilization of logistics vehicles, buildings, and base stations after being retired from vehicles. It is necessary to further improve the service life of lithium-ion batteries.
但是，由于锂离子电池负极活性材料主要为石墨负极，而石墨负极的嵌锂电位低于有机电解液，如PC、EC、DEC的还原电位。因此，在首次充电过程中会还原电解液而在负极表面生成一层固体电解质膜(SEI)，这个过程不仅有电子参与，同时也有锂离子参与。例如生成LiF、Li 2CO 3即烷基碳酸锂等含锂有机物。由于在锂离子电池中石墨负极并不含有锂，正极作为形成SEI过程中的唯一供锂源，将会导致7％-15％的活性锂损失，进而影响动力电池的能量密度和使用寿命。 However, since the negative electrode active material of lithium-ion batteries is mainly graphite negative electrode, the lithium intercalation potential of graphite negative electrode is lower than the reduction potential of organic electrolytes, such as PC, EC, and DEC. Therefore, during the first charging process, the electrolyte will be reduced to form a solid electrolyte film (SEI) on the surface of the negative electrode. This process not only involves electrons, but also lithium ions. For example, lithium-containing organic substances such as LiF, Li 2 CO 3 , such as alkyl lithium carbonate, are generated. Since the graphite negative electrode does not contain lithium in lithium-ion batteries, the positive electrode, as the only source of lithium in the formation of SEI, will cause a loss of 7%-15% of active lithium, which will affect the energy density and service life of the power battery.
为了提升动力电池的能量密度和使用寿命，广泛的补锂技术研究提供了多种的解决方案。例如，通过浆料补锂，即将金属锂或含有锂的有机物、改性材料等、负极材料和非水液体混合形成浆料，将浆料涂到集流体上，然后经干燥、 辊压、注液等工序。该方法虽然能提高锂离子电池能量密度，但金属锂反应活性高，极易与空气中的氧气以及水分发生反应。因此，在制备过程中对水分的控制要求也极为苛刻，从而增加了工艺难度。同时，由于锂离子电池对各种材料纯度要求极高，所用含锂材料一旦引入杂质，将会对电池性能造成不良影响。或者通过进行表面处理的稳定金属锂粉，但受限于其活性太高，难以使用锂离子电池制程前工序的操作时间。同时，锂粉容易飘浮在空气中，存在较大安全隐患。或者采用富锂的锂盐、锂氧化物、含锂有机物等材料在正极进行材料层级补锂，但由于补锂材料的活性问题，以及锂锂离子的利用率问题，给实际应用带来较大困难。In order to improve the energy density and service life of power batteries, extensive lithium supplementation technology research has provided a variety of solutions. For example, lithium supplementation through slurry, that is, metal lithium or lithium-containing organic matter, modified materials, etc., negative electrode materials and non-aqueous liquids are mixed to form a slurry, the slurry is coated on the current collector, and then dried, rolled, injected, etc. Liquid and other processes. Although this method can improve the energy density of lithium-ion batteries, metal lithium has high reactivity and is very easy to react with oxygen and moisture in the air. Therefore, the requirements for moisture control in the preparation process are also extremely strict, thereby increasing the difficulty of the process. At the same time, since lithium-ion batteries have extremely high requirements on the purity of various materials, once impurities are introduced into the lithium-containing materials used, it will have a negative impact on battery performance. Or through surface-treated stable metal lithium powder, but limited by its high activity, it is difficult to use the operating time of the lithium-ion battery process. At the same time, lithium powder is easy to float in the air, posing a great safety hazard. Or use lithium-rich lithium salts, lithium oxides, lithium-containing organic materials and other materials to supplement lithium at the material level at the positive electrode. difficulty.
现有技术公开了一种极片补锂方法及***，通过采用对金属锂片或锂带增加基材，一方面增强了锂带的强度，另一方面也在锂带与复合装置之间形成阻隔，使锂带在输送过程中不会与复合装置直接接触，因此避免了锂带在生产过程中被扯断或夹断。但此种方法对制造过程中的环境要求极高，以避免金属锂与空气、水发生反应，所以实际应用难度较高。The prior art discloses a method and system for replenishing lithium on a pole piece. By adding a base material to a metal lithium sheet or a lithium strip, on the one hand, the strength of the lithium strip is enhanced, and on the other hand, a lithium strip is formed between the lithium strip and the composite device. Barrier, so that the lithium ribbon will not be in direct contact with the composite device during the transportation process, thus avoiding the lithium ribbon being torn or pinched during the production process. However, this method has extremely high environmental requirements in the manufacturing process to avoid the reaction of metal lithium with air and water, so it is difficult to apply in practice.
现有技术还公开了负极补锂浆料、负极及锂二次电池，通过采用金属锂粉及预聚体制成补锂浆料，并涂布与已制备完成的负极极片上，再利用光照或加热等条件使补锂浆料中的预聚体发生聚合反应形成大分子聚合物，然后进行冷压制片得到补锂的负极极片。但此种方法增加了锂离子电池的制成复杂度，而且金属锂粉及预聚体的补锂浆料的均一性及量产过程中的分散度难以保持均一，容易发生沉降导致制成后的电芯一致性降低。The prior art also discloses negative electrode lithium supplement slurry, negative electrode and lithium secondary battery. Lithium supplement slurry is prepared by using metal lithium powder and prepolymer, and coated on the prepared negative electrode sheet, and then used light or Heating and other conditions cause the prepolymer in the lithium-replenishing slurry to undergo a polymerization reaction to form a macromolecular polymer, and then perform cold pressing to obtain a lithium-replenishing negative electrode sheet. However, this method increases the complexity of making lithium-ion batteries, and it is difficult to maintain the uniformity of the lithium-supplementing slurry of metal lithium powder and prepolymer and the dispersion in the mass production process, and it is prone to sedimentation, resulting in The battery cell consistency is reduced.
现有技术还公开了一种向锂离子电池正极片补锂的方法，通过将均匀有机锂溶液喷洒或滴加在正极片的表面，实现了“湿法补锂”，从而有效地避免干法 补锂时金属锂粉在空气中的漂浮，保证生产安全，而且整个工序简单，成本较低，补锂的量可以通过喷洒或滴加的有机锂溶液的量、喷洒或滴加的时间来加以准确控制，以达到均匀补锂的目的，防止正极片的析锂和变形，提高电池的首次效率，进而提高电池的能量密度。但是此种方法补锂必须在惰性气氛中实施，以保证高活性的有机锂溶液的稳定性，所以实际应用难度较高。The prior art also discloses a method of replenishing lithium to the positive electrode sheet of a lithium-ion battery. By spraying or dripping a uniform organic lithium solution on the surface of the positive electrode sheet, the "wet method lithium replenishment" is realized, thereby effectively avoiding the dry method. The metal lithium powder floats in the air during lithium supplementation to ensure production safety, and the whole process is simple and the cost is low. The amount of lithium supplementation can be adjusted by the amount of organic lithium solution sprayed or dripped, and the time of spraying or dripping Accurate control to achieve the purpose of uniform lithium supplementation, prevent lithium deposition and deformation of the positive plate, improve the first-time efficiency of the battery, and then increase the energy density of the battery. However, this method of lithium supplementation must be implemented in an inert atmosphere to ensure the stability of the highly active organic lithium solution, so it is difficult to apply in practice.
发明内容Contents of the invention
本发明的目的就在于针对上述现有技术的不足，提供一种高能量密度正极材料，还提供一种正极极片和锂离子电池，主要解决锂离子电池现有补锂方式效率低，操作过程复杂，且具有一定的安全隐患的问题。The purpose of the present invention is to address the deficiencies of the above-mentioned prior art, to provide a high energy density positive electrode material, and to provide a positive electrode sheet and a lithium-ion battery, mainly to solve the problem of low efficiency of the existing lithium-replenishing methods of lithium-ion batteries. It is complex and has certain security risks.
本发明的目的是通过以下技术方案实现的：The purpose of the present invention is achieved by the following technical solutions:
一种高能量密度正极材料，所述正极材料中含有正极活性物质和添加剂，所述添加剂为Li 2NixMyO 2@LFP-X的核壳材料，即在Li 2Ni xM yO 2材料外部通过物理或化学包覆一层LFP-X材料；其中，0＜x≤1，y＝1-x，M为Cu、Al、Fe、Mn、Co、Ti、Sb、Mg等金属元素，或B、F等非金属元素。进一步地，所述LFP-X壳材料为纯相LiFePO4材料或纯相LiFePO4进行金属掺杂的LFP-X材料，其中X可以为Mg、Mn、Al、Ti、V、Nb、Sb等金属。 A high-energy-density positive electrode material, the positive electrode material contains positive electrode active materials and additives , and the additive is the core-shell material of Li 2 NixMyO 2 @LFP-X, that is, passing through the outside of the Li 2 NixMyO 2 material Physically or chemically coat a layer of LFP-X material; where, 0<x≤1, y=1-x, M is Cu, Al, Fe, Mn, Co, Ti, Sb, Mg and other metal elements, or B, F and other non-metallic elements. Further, the LFP-X shell material is a pure-phase LiFePO4 material or a pure-phase LiFePO4 metal-doped LFP-X material, wherein X can be metals such as Mg, Mn, Al, Ti, V, Nb, Sb, etc.
进一步地，所述Li 2Ni xM yO 2@LFP-X材料，通过化学方法或物理方法制成，Li 2NixMyO 2@LFP-X材料的粒径为1-10um，其中Li 2NixMyO 2的核材料的粒径为0.5-9.5um，LFP-X壳材料的粒径为0.5-5um。 Further, the Li 2 NixMyO 2 @LFP-X material is made by chemical or physical methods, and the particle size of the Li 2 NixMyO 2 @LFP-X material is 1-10um, wherein Li 2 NixMyO 2 The particle size of the core material is 0.5-9.5um, and the particle size of the LFP-X shell material is 0.5-5um.
更进一步地，所述化学方法为固相法或液相法，所述固相法选用高温固相反应法、碳热还原法、微波合成发和脉冲激光沉积法合成、溶胶凝胶法、水热 合成法、沉淀法及溶剂热合成法；所述物理方法选用高能球磨、物理气相沉积方法。Furthermore, the chemical method is a solid-phase method or a liquid-phase method, and the solid-phase method is selected from high-temperature solid-phase reaction method, carbothermal reduction method, microwave synthesis and pulsed laser deposition synthesis, sol-gel method, water Thermal synthesis method, precipitation method and solvothermal synthesis method; the physical method is selected from high-energy ball milling and physical vapor deposition method.
进一步地，所述Li 2Ni xM yO 2@LFP-X材料在制备过程中选用的锂源为Li 2CO 3、LiOH、Li 2O、CH 3COOLi、LiNO 3和Li 2C 2O 4中的一种或多种，铁源为Fe 2O 3、FeOOH、Fe(OH) 3、Fe(NO3) 3、Fe 2(SO4) 3中的一种或多种，镍源为NiO、NiO 2、NiOOH、Ni(OH) 2、NiNO 3、Ni 2SO 4中的一种或多种，金属源，即M为Cu、Al、Fe、Mn、Co、Ti、Sb、Mg等金属元素时，使用MOx、MO(OH)x、M(NO 3)x、M(SO 4)x中的一种或多种，其中x取决于金属元素的价态。 Further, the Li 2 Ni x My O 2 @LFP-X material is selected as Li 2 CO 3 , LiOH, Li 2 O, CH 3 COOLi, LiNO 3 and Li 2 C 2 O lithium sources during the preparation process. One or more of 4 , the iron source is one or more of Fe 2 O 3 , FeOOH, Fe(OH) 3 , Fe(NO3) 3 , Fe 2 (SO4) 3 , the nickel source is NiO, One or more of NiO 2 , NiOOH, Ni(OH) 2 , NiNO 3 , Ni 2 SO 4 , metal source, that is, M is Cu, Al, Fe, Mn, Co, Ti, Sb, Mg and other metal elements When , use one or more of MOx, MO(OH)x, M(NO 3 )x, M(SO 4 )x, where x depends on the valence state of the metal element.
一种正极极片，包括金属集流体和高能量密度正极材料，添加剂直接与正极活性物质一起涂覆在金属集流体上，或在具有正极活性物质的极片上喷涂微米级别厚度的添加剂。A positive electrode sheet, including a metal current collector and a high energy density positive electrode material, the additive is directly coated on the metal current collector together with the positive electrode active material, or the additive with a thickness of micron is sprayed on the electrode sheet with the positive electrode active material.
进一步地，所述添加剂与正极活性材料的质量百分比为a，0％＜a≤50％。Further, the mass percentage of the additive and the positive electrode active material is a, 0%<a≤50%.
更进一步地，所述添加剂与正极活性材料的质量百分比为5％-15％。Furthermore, the mass percentage of the additive and the positive electrode active material is 5%-15%.
更进一步地，所述添加剂采用制备成浆料后，通过喷涂法、丝网印刷法、刮涂法涂布于正极活性材料极片表面，厚度为1-10um。Furthermore, after the additive is prepared into a slurry, it is coated on the surface of the positive electrode active material sheet by spraying, screen printing, or doctor blade, with a thickness of 1-10 um.
一种锂离子电池，所述锂离子电池包括电池壳、极芯和电解液，所述极芯和电解液密封在电池壳内，所述极芯包括正极、负极、以及位于正极和负极之间的隔膜，所述正极包括正极集流体和位于正极集流体上的高能量密度正极材料。A lithium-ion battery, the lithium-ion battery includes a battery case, a pole core and an electrolyte, the pole core and the electrolyte are sealed in the battery case, the pole core includes a positive pole, a negative pole, and a battery between the positive pole and the negative pole The separator, the positive electrode includes a positive electrode current collector and a high energy density positive electrode material on the positive electrode current collector.
与现有技术相比，本发明的有益效果是：Compared with prior art, the beneficial effect of the present invention is:
1、本发明提供了一种高能量密度正极材料、极片和锂离子电池，本发明在正极材料中采用特定种类的添加剂为Li 2Ni xM yO 2@LFP-X的核壳材料，其中 Li 2Ni xM yO 2具有极高的理论比容量和实际比容量，可达到300-600mAh/g； 1. The present invention provides a high-energy-density positive electrode material, a pole piece and a lithium-ion battery. The present invention uses a specific type of additive in the positive electrode material as a core-shell material of Li 2 Ni x My O 2 @LFP-X, Among them, Li 2 Ni x My O 2 has extremely high theoretical specific capacity and actual specific capacity, which can reach 300-600mAh/g;
2、同时，在充电脱锂后，由于富锂材料结构破坏，部分锂离子在放电是无法回嵌，因此具有较高的充电容量和较低的放电容量，从而实现利用其不可逆容量的活性锂补充负极SEI膜的消耗；2. At the same time, after charging and delithiation, due to the destruction of the structure of the lithium-rich material, some lithium ions cannot be reintercalated during discharge, so it has a higher charge capacity and a lower discharge capacity, so as to realize the use of active lithium with its irreversible capacity Supplement the consumption of negative electrode SEI film;
3、添加剂材料的剩余可逆容量使其在电池使用过程中又可以充当正极活性物质，实现动力电池能量密度的提升和寿命的延长；3. The remaining reversible capacity of the additive material enables it to act as a positive electrode active material during battery use, which improves the energy density and life of the power battery;
4、另外，由于在Li 2Ni xM yO 2材料外部通过物理或化学包覆一层LFP-X材料,保证了添加剂可以在锂离子电池生产过程中与一般正极活性物质的加工方法相同，既可以直接与正极活性物质一起涂覆在正极金属集流体上，或在具有正极活性物质的极片上喷涂微米级别厚度的添加剂材料制成高能量密度的正极极片，无需提供额外的制造工序或环境控制，在实际生产中更容易实现，避免了一般补锂技术的安全隐患的问题。 4. In addition, because a layer of LFP-X material is physically or chemically coated on the outside of the Li 2 Ni x My O 2 material, it is ensured that the additive can be processed in the same way as the general positive active material in the production process of lithium-ion batteries. It can be directly coated on the positive electrode metal current collector together with the positive electrode active material, or sprayed on the electrode sheet with the positive electrode active material to make a high energy density positive electrode sheet without additional manufacturing processes or Environmental control is easier to implement in actual production and avoids the safety hazards of general lithium supplementation technology.
附图说明Description of drawings
为了更清楚地说明本发明实施例的技术方案，下面将对实施例中所需要使用的附图作简单地介绍，应当理解，以下附图仅示出了本发明的某些实施例，因此不应被看作是对范围的限定，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其他相关的附图。In order to illustrate the technical solutions of the embodiments of the present invention more clearly, the accompanying drawings used in the embodiments will be briefly introduced below. It should be understood that the following drawings only show some embodiments of the present invention, and thus It should be regarded as a limitation on the scope, and those skilled in the art can also obtain other related drawings based on these drawings without creative work.
图1为Li 2Ni xM yO 2@LFP-X的核壳材料示意图； Figure 1 is a schematic diagram of the core-shell material of Li 2 Ni x M y O 2 @LFP-X;
图2为高能量密度正极极片示意图；Figure 2 is a schematic diagram of a high energy density positive pole piece;
图3锂离子电池首次充放电曲线。Figure 3 Lithium-ion battery charge and discharge curve for the first time.
具体实施方式Detailed ways
下面结合实施例对本发明作进一步说明：The present invention will be further described below in conjunction with embodiment:
下面结合附图和实施例对本发明作进一步的详细说明。可以理解的是，此处所描述的具体实施例仅仅用于解释本发明，而非对本发明的限定。另外还需要说明的是，为了便于描述，附图中仅示出了与本发明相关的部分而非全部结构。The present invention will be further described in detail below in conjunction with the accompanying drawings and embodiments. It should be understood that the specific embodiments described here are only used to explain the present invention, but not to limit the present invention. In addition, it should be noted that, for the convenience of description, only some structures related to the present invention are shown in the drawings but not all structures.
应注意到：相似的标号和字母在下面的附图中表示类似项，因此，一旦某一项在一个附图中被定义，则在随后的附图中不需要对其进行进一步定义和解释。同时，在本发明的描述中，术语“第一”、“第二”等仅用于区分描述，而不能理解为指示或暗示相对重要性。It should be noted that like numerals and letters denote similar items in the following figures, therefore, once an item is defined in one figure, it does not require further definition and explanation in subsequent figures. Meanwhile, in the description of the present invention, the terms "first", "second", etc. are only used to distinguish descriptions, and cannot be understood as indicating or implying relative importance.
如图1所示，本发明提供一种高能量密度正极材料，所述的正极材料中含有正极活性物质和添加剂，所述添加剂为Li 2NixMyO 2@LFP-X的核壳材料，即在Li 2Ni xM yO 2材料外部通过物理或化学包覆一层LFP-X材料。其中，0＜x≤1，y＝1-x，M为Cu、Al、Fe、Mn、Co、Ti、Sb、Mg等金属元素，或B、F等非金属元素，以实现其比容量达到可达到300-600mAh/g，甚至更高。 As shown in Figure 1, the present invention provides a high-energy-density positive electrode material. The positive electrode material contains positive electrode active materials and additives, and the additive is a core-shell material of Li 2 NixMyO 2 @LFP-X, that is, in Li 2 The Ni x M y O 2 material is physically or chemically coated with a layer of LFP-X material. Among them, 0<x≤1, y=1-x, M is Cu, Al, Fe, Mn, Co, Ti, Sb, Mg and other metal elements, or B, F and other non-metallic elements, in order to achieve its specific capacity up to It can reach 300-600mAh/g, or even higher.
同时，在充电脱锂后，由于富锂材料结构破坏，部分锂离子在放电是无法回嵌，因此具有较高的充电容量和较低的放电容量，从而实现利用其不可逆容量的活性锂补充负极SEI膜的消耗。At the same time, after charging and delithiation, due to the destruction of the structure of the lithium-rich material, some lithium ions cannot be reintercalated during discharge, so it has a higher charge capacity and a lower discharge capacity, so as to realize the use of its irreversible capacity to supplement the negative electrode with active lithium. Depletion of the SEI film.
所述添加剂的剩余可逆容量使其在电池使用过程中又可以充当正极活性物质，实现动力电池能量密度的提升和寿命的延长。所述添加剂由于在Li 2Ni xM yO 2材料外部通过物理或化学包覆一层LFP-X材料，保证了添加剂在空气中的稳定性，保存或制造过程中可实现与一般正极活性物质的加工方法相同。 The remaining reversible capacity of the additive enables it to act as a positive electrode active material during battery use, so as to improve the energy density and prolong the service life of the power battery. The additive is physically or chemically coated with a layer of LFP-X material on the outside of the Li 2 Ni x My O 2 material, which ensures the stability of the additive in the air, and can be compared with general positive active materials during storage or manufacturing. The processing method is the same.
所述LFP-X壳材料，可以为纯相LiFePO4材料，也可以为纯相LiFePO4进行金属掺杂的LFP-X材料，其中X可以为Mg、Mn、Al、Ti、V、Nb、Sb等金属，以提高纯相LiFePO4晶体内部的导电性能。The LFP-X shell material can be a pure phase LiFePO4 material, or a pure phase LiFePO4 metal-doped LFP-X material, wherein X can be Mg, Mn, Al, Ti, V, Nb, Sb and other metals , to improve the electrical conductivity inside the pure-phase LiFePO4 crystal.
所述Li 2Ni xM yO 2@LFP-X材料，可以通过化学方法，如固相法，即高温固相反应法、碳热还原法、微波合成发和脉冲激光沉积法合成；或液相法，如溶胶凝胶法、水热合成法、沉淀法及溶剂热合成法。也可以通过物理方法，如高能球磨、物理气相沉积等方法。Li 2NixMyO 2@LFP-X材料粒径1-10um，其中Li 2NixMyO 2的核材料粒径0.5-9.5um，LFP-X壳材料粒径0.5-5um。 The Li 2 Ni x M y O 2 @LFP-X material can be synthesized by chemical methods, such as solid-phase method, that is, high-temperature solid-phase reaction method, carbothermal reduction method, microwave synthesis and pulsed laser deposition method; or liquid Phase methods, such as sol-gel method, hydrothermal synthesis method, precipitation method and solvothermal synthesis method. Physical methods can also be used, such as high energy ball milling, physical vapor deposition and other methods. The particle size of the Li 2 NixMyO 2 @LFP-X material is 1-10um, of which the particle size of the core material of Li 2 NixMyO 2 is 0.5-9.5um, and the particle size of the LFP-X shell material is 0.5-5um.
所述Li 2Ni xM yO 2@LFP-X材料在制备过程中选用的锂源可以为Li 2CO 3、LiOH、Li 2O、CH 3COOLi、LiNO 3和Li 2C 2O 4中的一种或多种。 The Li 2 Ni x M y O 2 @LFP-X material can be selected as a lithium source in the preparation process of Li 2 CO 3 , LiOH, Li 2 O, CH 3 COOLi, LiNO 3 and Li 2 C 2 O 4 one or more of.
所述L Li 2Ni xM yO 2@LFP-X材料在制备过程中选用的铁源可以为Fe 2O 3、FeOOH、Fe(OH) 3、Fe(NO3) 3、Fe 2(SO4) 3中的一种或多种。 The iron source selected in the preparation process of the L Li 2 Ni x M y O 2 @LFP-X material can be Fe 2 O 3 , FeOOH, Fe(OH) 3 , Fe(NO3) 3 , Fe 2 (SO4) One or more of 3 .
所述Li 2Ni xM yO 2@LFP-X材料在制备过程中选用的镍源可以为NiO、NiO 2、NiOOH、Ni(OH) 2、NiNO 3、Ni 2SO 4中的一种或多种。 The nickel source selected in the preparation process of the Li 2 Ni x My O 2 @LFP-X material can be one of NiO, NiO 2 , NiOOH, Ni(OH) 2 , NiNO 3 , Ni 2 SO 4 or Various.
所述Li 2Ni xM yO 2@LFP-X材料在制备过程中选用的金属源，即M为Cu、Al、Fe、Mn、Co、Ti、Sb、Mg等金属元素时，可以使用MOx、MO(OH)x、M(NO 3)x、M(SO 4)x中的一种或多种，其中x取决于金属元素的价态。 The metal source selected in the preparation process of the Li 2 Ni x M y O 2 @LFP-X material, that is, when M is a metal element such as Cu, Al, Fe, Mn, Co, Ti, Sb, Mg, etc., MOx can be used One or more of , MO(OH)x, M(NO 3 )x, M(SO 4 )x, where x depends on the valence state of the metal element.
所述添加剂与正极活性材料一起进行浆料制备、涂覆在正极金属集流体上，其中，添加剂与正极活性材料的质量百分比为a，0％＜a≤50％，优选5％-15％，以上关于浆料制备、涂覆工艺与行业已知通用技术相同，无需格外环境控制及工艺工序，如图2所示。The additive is prepared together with the positive electrode active material and coated on the positive electrode metal current collector, wherein the mass percentage of the additive and the positive electrode active material is a, 0%<a≤50%, preferably 5%-15%, The above slurry preparation and coating process are the same as the known general technology in the industry, and there is no need for additional environmental control and process procedures, as shown in Figure 2.
所述添加剂材料采用行业已知通用技术制备成浆料，通过喷涂法、丝网印刷法、刮涂法涂布于正极活性材料极片表面，厚度为1-10um，如图2。The additive material is prepared into a slurry using a known general technology in the industry, and is coated on the surface of the positive electrode active material electrode sheet by spraying, screen printing, or scraping, with a thickness of 1-10 um, as shown in Figure 2.
本发明提供了一种高能量密度正极极片，该极片包括金属集流体和正极材料，添加剂可直接与正极活性物质一起涂覆在金属集流体上，或在具有正极活性物质的极片上喷涂微米级别1-10um厚度的添加剂材料。The invention provides a high-energy-density positive pole piece, the pole piece includes a metal current collector and a positive electrode material, the additive can be directly coated on the metal current collector together with the positive active material, or sprayed on the pole piece with the positive active material Additive materials with a thickness of 1-10um at the micron level.
所述添加剂稳定性高，粒径大小及表面能与一般正极材料类似，可实现直接与正极活性物质一起进行浆料制备、涂覆在正极金属集流体上，无需提供额外的制造工序或环境控制，在实际生产中更容易实现，同时避免了一般补锂技术的安全隐患的问题。The additive has high stability, and its particle size and surface energy are similar to those of general positive electrode materials. It can be directly prepared with the positive electrode active material and coated on the positive electrode metal current collector without additional manufacturing process or environmental control. , which is easier to realize in actual production, and at the same time avoids the safety hazards of general lithium supplementation technology.
所述添加剂可单独制成补锂浆料，在具有正极活性物质的极片上喷涂、转移涂布微米级别厚度的添加剂材料，厚度可为1-10um，在完成首次充电脱锂后，在极片的正极活性物质表面上形成稳定性更高的保护层，提升锂离子电池在滥用条件下的安全性，同时，单独的添加剂浆料保证了在极片上添加剂分布的一致性。The additive can be made into a lithium-supplementing slurry separately, and the additive material with a micron-level thickness can be sprayed and transferred on the pole piece with the positive active material, and the thickness can be 1-10um. After the first charge and delithiation are completed, the A more stable protective layer is formed on the surface of the positive electrode active material to improve the safety of lithium-ion batteries under abuse conditions. At the same time, the separate additive slurry ensures the consistency of additive distribution on the pole piece.
根据本发明的高能量密度正极材料及正极极片，可用于制备锂离子电池，所述正极材料为磷酸铁锂、钴酸锂、锰酸锂、镍酸锂、富锂锰基、镍钴锰三元、镍钴铝三元类，负极材料为石墨、金属锂、合金类。同时，可用于不同封装类型的锂离子电池，包括硬壳方型、软包和圆柱型。According to the high energy density positive electrode material and positive electrode sheet of the present invention, it can be used to prepare lithium-ion batteries, and the positive electrode material is lithium iron phosphate, lithium cobaltate, lithium manganate, lithium nickelate, lithium-rich manganese base, nickel-cobalt-manganese Ternary, nickel-cobalt-aluminum ternary type, the negative electrode material is graphite, metal lithium, alloy type. At the same time, it can be used for lithium-ion batteries of different packaging types, including hard-shell square, soft-pack and cylindrical.
本发明提供了一种锂离子电池，该锂离子电池包括电池壳、极芯和电解液，所述极芯和电解液密封在电池壳内，所述极芯包括正极、负极、以及位于正极和负极之间的隔膜，所述正极包括正极集流体和位于正极集流体上的正极材料，所述正极材料为本发明提供的正极材料。The invention provides a lithium-ion battery, the lithium-ion battery includes a battery case, a pole core and an electrolyte, the pole core and the electrolyte are sealed in the battery case, the pole core includes a positive pole, a negative pole, and a A separator between negative electrodes, the positive electrode includes a positive electrode collector and a positive electrode material on the positive electrode collector, and the positive electrode material is the positive electrode material provided by the present invention.
所述的锂离子电池采用本发明提供的正极材料，即含有正极活性物质和添加剂材料，通过与负极设计进行匹配计算，添加剂与正极活性材料的质量百分比为a，一般采用0％＜a≤50％，优选5％-15％。所述添加剂对正极材料没有种类要求，如行业通用的LFP、NCM、LMO、LTO等，应用范围广泛。The lithium-ion battery adopts the positive electrode material provided by the present invention, that is, contains positive electrode active material and additive material, and is calculated by matching with the design of the negative electrode. The mass percentage of the additive and the positive electrode active material is a, and generally 0%<a≤50 %, preferably 5%-15%. The additive has no requirement on the type of positive electrode material, such as LFP, NCM, LMO, LTO, etc. commonly used in the industry, and has a wide range of applications.
所述添加剂对负极材料没有种类要求，如行业通用的Gr、LTO、Gr-nano Si、Gr-SiO x等，应用范围广泛。 The additive has no requirement on the type of negative electrode material, such as Gr, LTO, Gr-nano Si, Gr- SiOx , etc. commonly used in the industry, and has a wide range of applications.
所述添加剂对隔膜材料没有种类要求，如行业通用的PP、PE、陶瓷涂覆、PVDF涂覆改性隔膜等，应用范围广泛。The additive has no requirement on the type of diaphragm material, such as PP, PE, ceramic coating, PVDF coating modified diaphragm, etc. commonly used in the industry, and has a wide range of applications.
所述添加剂对电解液材料没有种类要求，如行业通用的LiPF6、LiBOB、LiFSI电解质等及EC、DEC、DMC有机溶液等，应用范围广泛。The additives have no requirements on the type of electrolyte materials, such as LiPF6, LiBOB, LiFSI electrolytes commonly used in the industry, and EC, DEC, DMC organic solutions, etc., and have a wide range of applications.
相较于现有技术，本申请的高能量密度正极材料、极片和锂离子电池至少有如下改进：Compared with the prior art, the high energy density cathode material, pole piece and lithium ion battery of the present application have at least the following improvements:
1、添加剂含量明显提升，大幅提升补锂效率，同时使得锂离子电池的能量密度和寿命大幅提升。1. The content of additives is significantly increased, which greatly improves the efficiency of lithium supplementation, and at the same time greatly improves the energy density and life of lithium-ion batteries.
2、补锂添加剂材料稳定性明显提高，相较于含有金属锂带、锂粉的原材料，避免了安全隐患的问题。2. The stability of the lithium supplement additive material is significantly improved. Compared with the raw materials containing metal lithium strips and lithium powder, it avoids the problem of potential safety hazards.
3、加工工艺相较于其他补锂方法的制程工艺复杂度明显降低。无需提供额外的制造工序或环境控制，在实际生产中更容易实现。3. Compared with other lithium supplementation methods, the processing technology complexity is significantly reduced. There is no need to provide additional manufacturing processes or environmental controls, and it is easier to implement in actual production.
实施例1Example 1
以摩尔比为1-1.5:1比例混合Li 2O、NiO为原材料，在氩气保护环境下进行烧结，加热速度为5℃/min，烧结温度为600-800℃，烧结时间为5-15h，即可得到Li 2NiO 2材料,然后在氩气保护环境下，与质量百分比为2％-5％的纳米LFP材料采 用高能球磨机混合5-20h，使纳米LFP材料在Li 2NiO 2才上形成一层均匀包覆，即得到Li 2NiO 2@LFP材料。 Mix Li 2 O and NiO with a molar ratio of 1-1.5:1 as raw materials, and sinter in an argon-protected environment with a heating rate of 5°C/min, a sintering temperature of 600-800°C, and a sintering time of 5-15h , Li 2 NiO 2 material can be obtained, and then in an argon-protected environment, mix it with a nano-LFP material with a mass percentage of 2%-5% for 5-20h using a high-energy ball mill to make the nano-LFP material on Li 2 NiO 2 A uniform coating is formed to obtain Li 2 NiO 2 @LFP material.
实施例2Example 2
以摩尔比为1-1.05:1比例混合Li 2CO 3和FePO 4为原材料，葡萄糖配比16％，添加0.5-2％的Mg 2(OH) 2CO 3，以乙醇为分散剂，球磨混合6-10h，在80-100℃条件下真空烘干后进行烧结，烧结温度为700-800℃，烧结时间为8-12h，即可得到LFP-Mg的壳材料，然后与质量百分比为95％-98％的Li 2Ni 0.5Cu 0.5O 2材料用高能球磨机混合5-20h，即可得到Li 2Ni 0.5Cu 0.5O 2@LFP-Mg材料。 Mix Li 2 CO 3 and FePO 4 with a molar ratio of 1-1.05:1 as raw materials, glucose ratio 16%, add 0.5-2% Mg 2 (OH) 2 CO 3 , use ethanol as dispersant, and mix by ball milling 6-10h, after vacuum drying at 80-100°C, sintering, the sintering temperature is 700-800°C, and the sintering time is 8-12h, the shell material of LFP-Mg can be obtained, and then the mass percentage is 95% The -98% Li 2 Ni 0.5 Cu 0.5 O 2 material is mixed with a high-energy ball mill for 5-20 hours to obtain the Li 2 Ni 0.5 Cu 0.5 O 2 @LFP-Mg material.
实施例3Example 3
以质量比为1.05-1.15:1比例混合Li 2NiO 2@LFP和LFP为原材料，其中Li 2NiO＝@LFP为添加剂，LFP为正极活性材料，再添加0.5-1％的导电剂SP和粘接剂PVDF，以NMP为分散剂，采用行星搅拌混合3-5h，制备成正极材料浆料，并采用转移涂布方式在12um厚度的铝箔上涂布压实际密度为2.4-2.5mg/m2的高能量正极材料极片。 Mix Li 2 NiO 2 @LFP and LFP as raw materials with a mass ratio of 1.05-1.15:1, where Li 2 NiO=@LFP is an additive, LFP is a positive electrode active material, and then add 0.5-1% conductive agent SP and viscose Adhesive PVDF, using NMP as dispersant, using planetary agitation and mixing for 3-5h to prepare positive electrode material slurry, and using transfer coating method to coat and compress the actual density of 2.4-2.5mg/m2 on aluminum foil with a thickness of 12um High-energy cathode material pole piece.
实施例4Example 4
制备锂离子电池，利用实施例3中的高能量正极材料极片、石墨负极及隔膜进行配制卷绕，制备得到裸电芯，再将裸电芯入壳、注液，之后在25℃的环境下静置，待电解液浸润后进行化成、整形、除气工艺，最终得到高能量密度的锂离子电池，并且在化成测试阶段可以发现其首次效率＞99％，如图3。To prepare a lithium-ion battery, use the high-energy positive electrode material pole piece, graphite negative electrode, and separator in Example 3 to prepare and wind up to prepare a bare cell, then put the bare cell into the shell, inject liquid, and then place the battery in an environment of 25°C After standing still, the formation, shaping and degassing processes are carried out after the electrolyte is infiltrated, and finally a lithium-ion battery with high energy density is obtained, and its first efficiency can be found to be >99% in the formation test stage, as shown in Figure 3.
如图3所示，相比于未补锂电池，含有Li2NiO2@LFP添加剂的锂离子电池首次效率＞99％。As shown in Figure 3, compared with the unsupplemented lithium battery, the lithium-ion battery containing Li2NiO2@LFP additive has a first-time efficiency of >99%.
注意，上述仅为本发明的较佳实施例及所运用技术原理。本领域技术人员会理解，本发明不限于这里所述的特定实施例，对本领域技术人员来说能够进行各种明显的变化、重新调整和替代而不会脱离本发明的保护范围。因此，虽然通过以上实施例对本发明进行了较为详细的说明，但是本发明不仅仅限于以上实施例，在不脱离本发明构思的情况下，还可以包括更多其他等效实施例，而本发明的范围由所附的权利要求范围决定。Note that the above are only preferred embodiments of the present invention and applied technical principles. Those skilled in the art will understand that the present invention is not limited to the specific embodiments described herein, and that various obvious changes, rearrangements and substitutions can be made by those skilled in the art without departing from the protection scope of the present invention. Therefore, although the present invention has been described in detail through the above embodiments, the present invention is not limited to the above embodiments, and can also include more other equivalent embodiments without departing from the concept of the present invention, and the present invention The scope is determined by the scope of the appended claims.

Claims (10)

  1. 一种高能量密度正极材料，其特征在于：所述正极材料中含有正极活性物质和添加剂，所述添加剂为Li 2NixMyO 2@LFP-X的核壳材料，即在Li 2Ni xM yO 2材料外部通过物理或化学包覆一层LFP-X材料；其中，0＜x≤1，y＝1-x，M为Cu、Al、Fe、Mn、Co、Ti、Sb、Mg等金属元素，或B、F等非金属元素。 A high energy density positive electrode material, characterized in that: the positive electrode material contains a positive electrode active material and an additive, and the additive is a core-shell material of Li 2 NixMyO 2 @LFP-X, that is, in Li 2 Ni x My O 2 The outside of the material is physically or chemically coated with a layer of LFP-X material; where, 0<x≤1, y=1-x, M is Cu, Al, Fe, Mn, Co, Ti, Sb, Mg and other metal elements , or B, F and other non-metallic elements.
  2. 根据权利要求1所述的一种高能量密度正极材料，其特征在于：所述LFP-X壳材料为纯相LiFePO4材料或纯相LiFePO4进行金属掺杂的LFP-X材料，其中X可以为Mg、Mn、Al、Ti、V、Nb、Sb等金属。A high energy density positive electrode material according to claim 1, characterized in that: the LFP-X shell material is a pure phase LiFePO4 material or a pure phase LiFePO4 metal-doped LFP-X material, wherein X can be Mg , Mn, Al, Ti, V, Nb, Sb and other metals.
  3. 根据权利要求1所述的一种高能量密度正极材料，其特征在于：所述Li 2Ni xM yO 2@LFP-X材料，通过化学方法或物理方法制成，Li 2NixMyO 2@LFP-X材料的粒径为1-10um，其中Li 2NixMyO 2的核材料的粒径为0.5-9.5um，LFP-X壳材料的粒径为0.5-5um。 A high energy density cathode material according to claim 1, characterized in that : said Li 2 NixMyO 2 @LFP-X material is made by chemical or physical methods, Li 2 NixMyO 2 @LFP The particle size of the -X material is 1-10um, the particle size of the core material of Li 2 NixMyO 2 is 0.5-9.5um, and the particle size of the LFP-X shell material is 0.5-5um.
  4. 根据权利要求3所述的一种高能量密度正极材料，其特征在于：所述化学方法为固相法或液相法，所述固相法选用高温固相反应法、碳热还原法、微波合成发和脉冲激光沉积法合成、溶胶凝胶法、水热合成法、沉淀法及溶剂热合成法；所述物理方法选用高能球磨、物理气相沉积方法。A high-energy-density cathode material according to claim 3, characterized in that: the chemical method is a solid-phase method or a liquid-phase method, and the solid-phase method is selected from high-temperature solid-phase reaction method, carbothermal reduction method, microwave Synthesis and pulse laser deposition synthesis, sol-gel method, hydrothermal synthesis method, precipitation method and solvothermal synthesis method; the physical method is high-energy ball milling and physical vapor deposition method.
  5. 根据权利要求1所述的一种高能量密度正极材料，其特征在于：所述Li 2Ni xM yO 2@LFP-X材料在制备过程中选用的锂源为Li 2CO 3、LiOH、Li 2O、CH 3COOLi、LiNO 3和Li 2C 2O 4中的一种或多种，铁源为Fe 2O 3、FeOOH、Fe(OH) 3、Fe(NO3) 3、Fe 2(SO4) 3中的一种或多种，镍源为NiO、NiO 2、NiOOH、Ni(OH) 2、NiNO 3、Ni 2SO 4中的一种或多种，金属源，即M为Cu、Al、Fe、Mn、Co、Ti、Sb、Mg等金属元素时，使用MOx、MO(OH)x、M(NO 3)x、M(SO 4)x中的一种或多种，其中x取决于金属元素的价态。 A high energy density positive electrode material according to claim 1, characterized in that: the lithium source selected in the preparation process of the Li 2 Ni x My O 2 @LFP-X material is Li 2 CO 3 , LiOH, One or more of Li 2 O, CH 3 COOLi, LiNO 3 and Li 2 C 2 O 4 , the iron source is Fe 2 O 3 , FeOOH, Fe(OH) 3 , Fe(NO3) 3 , Fe 2 ( One or more of SO4) 3 , the nickel source is one or more of NiO, NiO 2 , NiOOH, Ni(OH) 2 , NiNO 3 , Ni 2 SO 4 , the metal source, that is, M is Cu, For metal elements such as Al, Fe, Mn, Co, Ti, Sb, Mg, use one or more of MOx, MO(OH)x, M(NO 3 )x, M(SO 4 )x, where x Depends on the valence state of the metal element.
  6. 一种正极极片，包括金属集流体和高能量密度正极材料，添加剂直接与正极活性物质一起涂覆在金属集流体上，或在具有正极活性物质的极片上喷涂微米级别厚度的添加剂。A positive electrode sheet, including a metal current collector and a high energy density positive electrode material, the additive is directly coated on the metal current collector together with the positive electrode active material, or the additive with a thickness of micron is sprayed on the electrode sheet with the positive electrode active material.
  7. 根据权利要求6所述的一种正极极片，其特征在于：所述添加剂与正极活性材料的质量百分比为a，0％＜a≤50％。The positive pole piece according to claim 6, characterized in that: the mass percentage of the additive and the positive active material is a, 0%<a≤50%.
  8. 根据权利要求6所述的一种正极极片，其特征在于：所述添加剂与正极活性材料的质量百分比为5％-15％。The positive pole piece according to claim 6, characterized in that: the mass percentage of the additive and the positive active material is 5%-15%.
  9. 根据权利要求6所述的一种正极极片，其特征在于：所述添加剂采用制备成浆料后，通过喷涂法、丝网印刷法、刮涂法涂布于正极活性材料极片表面，厚度为1-10um。A positive pole piece according to claim 6, characterized in that: after the additive is prepared into a slurry, it is coated on the surface of the positive pole active material pole piece by a spraying method, a screen printing method, or a doctor blade method, and the thickness 1-10um.
  10. 一种锂离子电池，其特征在于：所述锂离子电池包括电池壳、极芯和电解液，所述极芯和电解液密封在电池壳内，所述极芯包括正极、负极、以及位于正极和负极之间的隔膜，所述正极包括正极集流体和位于正极集流体上的高能量密度正极材料。A lithium-ion battery, characterized in that: the lithium-ion battery includes a battery case, a pole core and an electrolyte, the pole core and the electrolyte are sealed in the battery case, the pole core includes a positive pole, a negative pole, and a and a separator between the negative electrode, the positive electrode includes a positive electrode current collector and a high energy density positive electrode material on the positive electrode current collector.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116936967A (en) * 2023-09-18 2023-10-24 江苏正力新能电池技术有限公司 Lithium supplementing negative electrode piece and lithium battery

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114725369A (en) * 2022-02-10 2022-07-08 中国第一汽车股份有限公司 High-energy-density positive electrode material, positive electrode plate and lithium ion battery
CN116544533A (en) * 2022-10-09 2023-08-04 深圳市德方创域新能源科技有限公司 Positive electrode lithium supplementing additive, preparation method thereof, lithium-rich positive electrode and secondary battery

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103474625A (en) * 2013-08-05 2013-12-25 合肥国轩高科动力能源股份公司 Coating method for core-shell novel positive electrode material for lithium ion battery
CN108232343A (en) * 2018-01-04 2018-06-29 中南大学 Benefit lithium additive, benefit lithium anode and its preparation and application for lithium ion battery
CN111653770A (en) * 2020-06-10 2020-09-11 广东邦普循环科技有限公司 Positive electrode additive and preparation method and application thereof
CN111668470A (en) * 2020-06-19 2020-09-15 北京物科清能科技有限公司 Positive electrode lithium supplement material and preparation method and application thereof
CN112054166A (en) * 2019-06-06 2020-12-08 苏州第一元素纳米技术有限公司 Core-shell structure electrochemical active material, preparation method and battery
CN113328082A (en) * 2021-06-25 2021-08-31 珠海冠宇电池股份有限公司 Positive electrode lithium supplement material and lithium ion battery comprising same
WO2022109886A1 (en) * 2020-11-25 2022-06-02 宁德时代新能源科技股份有限公司 Composite positive electrode material and preparation method therefor, positive electrode plate, secondary battery and battery module comprising same, battery pack, and device
CN114725369A (en) * 2022-02-10 2022-07-08 中国第一汽车股份有限公司 High-energy-density positive electrode material, positive electrode plate and lithium ion battery
CN115312711A (en) * 2022-05-17 2022-11-08 深圳市德方创域新能源科技有限公司 Positive electrode composite material and preparation method and application thereof

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103904311B (en) * 2012-12-28 2016-05-18 国联汽车动力电池研究院有限责任公司 Lithium-rich manganese-based anode material that a kind of surface is coated compound and preparation method thereof
CN107968195A (en) * 2017-11-22 2018-04-27 合肥国轩高科动力能源有限公司 A kind of lithium-rich anode material of LiFePO4 cladding and preparation method thereof
CN110838573A (en) * 2018-08-16 2020-02-25 中国科学院物理研究所 Lithium ion energy storage device lithium supplement slurry and preparation method and application thereof
CN109786746A (en) * 2018-12-25 2019-05-21 深圳市比克动力电池有限公司 Positive plate, lithium ion cell positive mend lithium material and preparation method thereof
CN110854382B (en) * 2019-11-04 2021-04-13 宁德新能源科技有限公司 Positive electrode lithium supplement material, positive electrode containing positive electrode lithium supplement material and preparation method of positive electrode lithium supplement material
CN112038639A (en) * 2020-09-01 2020-12-04 福建巨电新能源股份有限公司 Lithium supplement slurry with core-shell structure and application thereof in lithium supplement modification of lithium ion battery anode
CN113991111B (en) * 2021-09-14 2023-08-29 陕西创普斯新能源科技有限公司 Lithium iron phosphate composite material with positive electrode lithium supplementing function and preparation method thereof
CN113991101A (en) * 2021-10-25 2022-01-28 江苏海基新能源股份有限公司 Lithium supplementing method for lithium iron phosphate lithium ion battery and lithium iron phosphate lithium ion battery

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103474625A (en) * 2013-08-05 2013-12-25 合肥国轩高科动力能源股份公司 Coating method for core-shell novel positive electrode material for lithium ion battery
CN108232343A (en) * 2018-01-04 2018-06-29 中南大学 Benefit lithium additive, benefit lithium anode and its preparation and application for lithium ion battery
CN112054166A (en) * 2019-06-06 2020-12-08 苏州第一元素纳米技术有限公司 Core-shell structure electrochemical active material, preparation method and battery
CN111653770A (en) * 2020-06-10 2020-09-11 广东邦普循环科技有限公司 Positive electrode additive and preparation method and application thereof
CN111668470A (en) * 2020-06-19 2020-09-15 北京物科清能科技有限公司 Positive electrode lithium supplement material and preparation method and application thereof
WO2022109886A1 (en) * 2020-11-25 2022-06-02 宁德时代新能源科技股份有限公司 Composite positive electrode material and preparation method therefor, positive electrode plate, secondary battery and battery module comprising same, battery pack, and device
CN113328082A (en) * 2021-06-25 2021-08-31 珠海冠宇电池股份有限公司 Positive electrode lithium supplement material and lithium ion battery comprising same
CN114725369A (en) * 2022-02-10 2022-07-08 中国第一汽车股份有限公司 High-energy-density positive electrode material, positive electrode plate and lithium ion battery
CN115312711A (en) * 2022-05-17 2022-11-08 深圳市德方创域新能源科技有限公司 Positive electrode composite material and preparation method and application thereof

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116936967A (en) * 2023-09-18 2023-10-24 江苏正力新能电池技术有限公司 Lithium supplementing negative electrode piece and lithium battery
CN116936967B (en) * 2023-09-18 2023-12-15 江苏正力新能电池技术有限公司 Lithium supplementing negative electrode piece and lithium battery

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