WO2023082182A1 - Matériau actif d'électrode positive, feuille d'électrode positive, batterie secondaire, module de batterie, bloc-batterie et dispositif électrique - Google Patents

Matériau actif d'électrode positive, feuille d'électrode positive, batterie secondaire, module de batterie, bloc-batterie et dispositif électrique Download PDF

Info

Publication number
WO2023082182A1
WO2023082182A1 PCT/CN2021/130350 CN2021130350W WO2023082182A1 WO 2023082182 A1 WO2023082182 A1 WO 2023082182A1 CN 2021130350 W CN2021130350 W CN 2021130350W WO 2023082182 A1 WO2023082182 A1 WO 2023082182A1
Authority
WO
WIPO (PCT)
Prior art keywords
positive electrode
active material
electrode active
optionally
phosphate
Prior art date
Application number
PCT/CN2021/130350
Other languages
English (en)
Chinese (zh)
Inventor
蒋耀
欧阳楚英
张欣欣
邓斌
赵旭山
王志强
袁天赐
刘少军
陈尚栋
徐波
Original Assignee
宁德时代新能源科技股份有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 宁德时代新能源科技股份有限公司 filed Critical 宁德时代新能源科技股份有限公司
Priority to CN202180093423.0A priority Critical patent/CN116964774A/zh
Priority to PCT/CN2021/130350 priority patent/WO2023082182A1/fr
Priority to PCT/CN2022/126778 priority patent/WO2023066386A1/fr
Priority to EP22882997.4A priority patent/EP4418362A1/fr
Priority to PCT/CN2022/126829 priority patent/WO2023066393A1/fr
Priority to CN202280007637.6A priority patent/CN116547835A/zh
Priority to CN202280013384.3A priority patent/CN116964781A/zh
Priority to JP2024515815A priority patent/JP2024533449A/ja
Priority to PCT/CN2022/126838 priority patent/WO2023066394A1/fr
Priority to KR1020247008222A priority patent/KR20240048003A/ko
Priority to JP2023543271A priority patent/JP2024505446A/ja
Priority to KR1020247007998A priority patent/KR20240046889A/ko
Priority to EP22882998.2A priority patent/EP4418363A1/fr
Priority to JP2024515538A priority patent/JP2024534988A/ja
Priority to KR1020237024611A priority patent/KR20230122108A/ko
Priority to AU2022371736A priority patent/AU2022371736A1/en
Priority to CN202280013385.8A priority patent/CN117121236A/zh
Priority to EP22882990.9A priority patent/EP4261946A1/fr
Publication of WO2023082182A1 publication Critical patent/WO2023082182A1/fr
Priority to US18/351,925 priority patent/US20230361296A1/en
Priority to US18/641,410 priority patent/US20240282969A1/en
Priority to US18/641,427 priority patent/US20240282963A1/en

Links

Images

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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present application relates to the technical field of lithium batteries, in particular to a positive electrode active material and a preparation method thereof, a positive electrode sheet containing the same, a secondary battery, a battery module, a battery pack and an electrical device.
  • lithium-ion batteries are widely used in various large-scale power devices, energy storage systems and various consumer products due to their excellent electrochemical performance, no memory effect, and low environmental pollution. Widely used in pure electric vehicles, hybrid electric vehicles and other new energy vehicles.
  • lithium manganese phosphate positive electrode active material has the advantages of high working voltage, wide range of raw material sources and less environmental pollution, and is considered to be the preferred positive electrode active material for lithium-ion batteries that is expected to replace lithium iron phosphate.
  • the cycle performance, high-temperature storage performance and safety performance of secondary batteries using lithium manganese phosphate cathode active materials have not been comprehensively improved, which greatly limits the wider application of lithium manganese phosphate batteries. Therefore, it is expected to design a lithium manganese phosphate secondary battery with high gram capacity, good cycle performance and safety performance.
  • the present application is made in view of the above problems, and its purpose is to provide a lithium manganese phosphate positive electrode active material, so that the secondary battery using the positive electrode active material has a higher gram capacity, good cycle performance and safety performance.
  • the present application provides a lithium manganese phosphate positive electrode active material and a preparation method thereof, as well as related positive electrode sheets, secondary batteries, battery modules, battery packs and electrical devices.
  • the first aspect of the present application provides a positive electrode active material with a core-shell structure, which includes an inner core and a shell covering the inner core,
  • the shell includes a first cladding layer covering the inner core and a second cladding layer covering the first cladding layer,
  • the first cladding layer includes pyrophosphate MP 2 O 7 and phosphate XPO 4 , wherein the M and X are each independently selected from Li, Fe, Ni, Mg, Co, Cu, Zn, Ti, One or more of Ag, Zr, Nb or Al;
  • the second cladding layer includes carbon.
  • the positive electrode active material of the present application can improve the gram capacity, cycle performance and safety performance of the secondary battery.
  • the lithium manganese phosphate positive electrode active material of the present application has a core-shell structure, wherein by doping the manganese site and phosphorus site of the lithium manganese phosphate core with element A and element R respectively, not only can effectively reduce The dissolution of manganese, thereby reducing the migration of manganese ions to the negative electrode, reducing the consumption of electrolyte due to the decomposition of the SEI film, improving the cycle performance and safety performance of the secondary battery, can also promote the adjustment of Mn-O bonds, and reduce the migration barrier of lithium ions.
  • the inner core by coating the inner core with the first coating layer including pyrophosphate and phosphate, the migration resistance of manganese can be further increased, its dissolution can be reduced, and the surface lithium impurities can be reduced. content, reduce the contact between the inner core and the electrolyte, thereby reducing the side reaction at the interface, reducing gas production, and improving the high-temperature storage performance, cycle performance and safety performance of the secondary battery; by further coating the carbon-containing layer as the second coating layer, The safety performance and dynamic performance of the secondary battery can be further improved.
  • the first coating layer including pyrophosphate and phosphate by coating the inner core with the first coating layer including pyrophosphate and phosphate, the migration resistance of manganese can be further increased, its dissolution can be reduced, and the surface lithium impurities can be reduced. content, reduce the contact between the inner core and the electrolyte, thereby reducing the side reaction at the interface, reducing gas production, and improving the high-temperature storage performance, cycle performance and safety performance of the secondary battery;
  • the interplanar spacing of the phosphate of the first cladding layer is 0.345-0.358nm, and the included angle of the crystal direction (111) is 24.25°-26.45°; the pyrophosphate of the first cladding layer The interplanar spacing is 0.293-0.326nm, and the included angle of the crystal direction (111) is 26.41°-32.57°.
  • the cycle performance and rate performance of the secondary battery are further improved.
  • the ratio of y to 1-y is 1:10 to 10:1, optionally 1:4 to 1:1.
  • the cycle performance and rate performance of the secondary battery are further improved.
  • the ratio of z to 1-z is 1:9 to 1:999, optionally 1:499 to 1:249.
  • the cycle performance and rate performance of the secondary battery are further improved.
  • the coating amount of the first coating layer is greater than 0% by weight and less than or equal to 7% by weight, optionally 4-5.6% by weight, based on the weight of the inner core.
  • the coating amount of the first coating layer is within the above range, the function of the first coating layer can be effectively exerted, and at the same time, the kinetic performance of the secondary battery will not be affected due to the over thickness of the coating layer.
  • the weight ratio of pyrophosphate to phosphate in the first coating layer is 1:3 to 3:1, optionally 1:3 to 1:1. Therefore, by using pyrophosphate and phosphate in a suitable weight ratio range, it can not only effectively hinder the dissolution of manganese, but also effectively reduce the content of lithium impurities on the surface and reduce the side reaction at the interface, thereby improving the high-temperature storage performance and safety performance of the secondary battery. and cycle performance.
  • the crystallinity of the pyrophosphate salt and the phosphate salt is independently 10%-100%, optionally 50%-100%. Therefore, the pyrophosphate and phosphate having the crystallinity in the above-mentioned range are conducive to fully exerting the functions of pyrophosphate to hinder manganese dissolution and phosphate to reduce the content of lithium impurities on the surface and reduce the side reaction at the interface.
  • the coating amount of the second coating layer is greater than 0% by weight and less than or equal to 6% by weight, optionally 3-5% by weight, based on the weight of the inner core. Therefore, the presence of the second coating layer can effectively reduce the contact between the active material in the coating layer and the electrolyte, reduce the corrosion of the active material by the electrolyte, and improve the conductivity of the positive electrode active material. When the coating amount of the second layer is within the above range, the gram capacity of the positive electrode active material can be effectively increased.
  • the A is selected from at least two of Fe, Ti, V, Ni, Co and Mg. Therefore, if A is two or more metals within the above range, doping at the manganese site is beneficial to enhance the doping effect, further reduce the surface oxygen activity, and thereby inhibit the dissolution of manganese.
  • the Li/Mn antisite defect concentration of the positive electrode active material is less than 4%, optionally less than 2%. Therefore, through the Li/Mn antisite defect concentration within the above range, Mn 2+ can be prevented from hindering the transport of Li + , and at the same time, the gram capacity and rate performance of the positive electrode active material can be improved.
  • the lattice change rate of the positive electrode active material is less than 6%, optionally less than 4%. Therefore, when the lattice change rate is within the above range, it is possible to avoid excessive interfacial stress from affecting Li + transport, thereby improving the rate performance of the secondary battery.
  • the surface oxygen valence state of the positive electrode active material is below -1.88, optionally between -1.98 and -1.88. Therefore, the surface oxygen valence state of the positive electrode material is within the above range, which can avoid the following situation that may be caused: because the surface oxygen valence state is too high, the ability to obtain electrons is too strong, resulting in increased interface side reactions with the electrolyte, thereby affecting the two.
  • the cycle performance and high temperature storage performance of the secondary battery is below -1.88, optionally between -1.98 and -1.88. Therefore, the surface oxygen valence state of the positive electrode material is within the above range, which can avoid the following situation that may be caused: because the surface oxygen valence state is too high, the ability to obtain electrons is too strong, resulting in increased interface side reactions with the electrolyte, thereby affecting the two.
  • the cycle performance and high temperature storage performance of the secondary battery is
  • the positive electrode active material has a compacted density at 3 tons (T) of 2.0 g/cm 3 or more, optionally 2.2 g/cm 3 or more. Therefore, if the compression density of the positive electrode active material is within the above range, the weight of the active material per unit volume is greater, which is more conducive to increasing the volumetric energy density of the secondary battery.
  • the second aspect of the present application provides a method for preparing a positive electrode active material, comprising the following steps:
  • the Said A is selected from one or more of Zn, Al, Na, K, Mg, Mo, W, Ti, V, Zr, Fe, Ni, Co, Ga, Sn, Sb, Nb and Ge, and may be One or more of Fe, Ti, V, Ni, Co and Mg
  • the R is selected from one or more of B, Si, N and S;
  • Coating step provide MP 2 O 7 powder and XPO 4 suspension containing carbon source, add the core material, MP 2 O 7 powder into XPO 4 suspension containing carbon source and mix, Sintering to obtain a positive electrode active material, wherein the M and X are each independently selected from one or more of Li, Fe, Ni, Mg, Co, Cu, Zn, Ti, Ag, Zr, Nb or Al;
  • the positive electrode active material has a core-shell structure, which includes an inner core and a shell covering the inner core, and the shell includes a first cladding layer covering the inner core and a shell covering the first cladding layer.
  • the second coating layer, the first coating layer includes pyrophosphate MP 2 O 7 and phosphate XPO 4 , and the second coating layer includes carbon.
  • the step of providing core material comprises the following steps:
  • Step (1) mixing and stirring a source of manganese, a source of element A, and an acid in a container to obtain manganese salt particles doped with element A;
  • the step (1) is carried out at a temperature of 20-120°C, optionally 25-80°C; and/or,
  • the stirring in the step (1) is carried out at 500-700 rpm for 60-420 minutes, optionally for 120-360 minutes.
  • the doping elements can be uniformly distributed, and the crystallinity of the material after sintering is higher, thereby improving the gram capacity and rate performance of the material.
  • the source of element A is selected from one or more of element A, sulfate, halide, nitrate, organic acid salt, oxide or hydroxide; and/or,
  • the source of the element R is selected from one or more of elemental R elements, sulfates, halides, nitrates, organic acid salts, oxides or hydroxides, and inorganic acids of element R. Therefore, by selecting the source of each dopant element within the above range, the performance of the material can be effectively improved.
  • the MP 2 O 7 powder is prepared by adding the source of element M and the source of phosphorus into a solvent to obtain a mixture, adjusting the pH of the mixture to 4-6, stirring and fully reacting, and then Obtained by drying and sintering, wherein M is selected from one or more of Li, Fe, Ni, Mg, Co, Cu, Zn, Ti, Ag, Zr, Nb or Al.
  • the drying step is drying at 100-300°C, optionally 150-200°C, for 4-8h.
  • the sintering step is sintering at 500-800° C., optionally 650-800° C., for 4-10 hours in an inert gas atmosphere.
  • the sintering temperature in the cladding step is 500-800° C., and the sintering time is 4-10 h. Therefore, by controlling the sintering temperature and time during cladding, the gram capacity and rate performance of the material can be further improved.
  • the preparation method described in this application has wide sources of raw materials, low cost and simple process, which is beneficial to realize industrialization.
  • the third aspect of the present application provides a positive electrode sheet, which includes a positive electrode current collector and a positive electrode film layer arranged on at least one surface of the positive electrode current collector, the positive electrode film layer includes the positive electrode active material described in the first aspect of the present application or by The positive electrode active material prepared by the method described in the second aspect of the present application, and the content of the positive electrode active material in the positive electrode film layer is more than 10% by weight, based on the total weight of the positive electrode film layer.
  • the content of the positive electrode active material in the positive electrode film layer is 90-99.5% by weight, based on the total weight of the positive electrode film layer.
  • the content of the positive electrode active material is within the above range, it is beneficial to give full play to the advantages of the positive electrode active material of the present application.
  • the fourth aspect of the application provides a secondary battery, which includes the positive electrode active material described in the first aspect of the application or the positive electrode active material prepared by the method described in the second aspect of the application or the positive electrode active material described in the third aspect of the application Positive pole piece.
  • a fifth aspect of the present application provides a battery module, which includes the secondary battery described in the fourth aspect of the present application.
  • a sixth aspect of the present application provides a battery pack, which includes the battery module described in the fifth aspect of the present application.
  • the seventh aspect of the present application provides an electric device, which includes at least one of the secondary battery described in the fourth aspect of the present application, the battery module described in the fifth aspect of the present application, or the battery pack described in the sixth aspect of the present application. A sort of.
  • the positive electrode sheet, secondary battery, battery module, battery pack and electrical device described in the present application include the lithium manganese phosphate positive electrode active material described in the present application, and thus have at least the same advantages as the lithium manganese phosphate positive electrode active material.
  • FIG. 1 is a schematic diagram of a positive electrode active material with a core-shell structure according to an embodiment of the present application.
  • Fig. 2 is a comparison chart of the XRD spectrum of Example 1-1 of the present application before the first coating layer and the second coating layer are not coated with the standard XRD spectrum of lithium manganese phosphate (00-033-0804).
  • FIG. 3 is a schematic diagram of a secondary battery according to an embodiment of the present application.
  • FIG. 4 is an exploded view of the secondary battery according to one embodiment of the present application shown in FIG. 3 .
  • FIG. 5 is a schematic diagram of a battery module according to an embodiment of the present application.
  • FIG. 6 is a schematic diagram of a battery pack according to an embodiment of the present application.
  • FIG. 7 is an exploded view of the battery pack according to one embodiment of the present application shown in FIG. 6 .
  • FIG. 8 is a schematic diagram of an electrical device in which a secondary battery is used as a power source according to an embodiment of the present application.
  • ranges disclosed herein are defined in terms of lower and upper limits, and a given range is defined by selecting a lower limit and an upper limit that define the boundaries of the specified range. Ranges defined in this manner may be inclusive or exclusive and may be combined arbitrarily, ie any lower limit may be combined with any upper limit to form a range. For example, if ranges of 60-120 and 80-110 are listed for a particular parameter, it is understood that ranges of 60-110 and 80-120 are contemplated. Additionally, if the minimum range values 1 and 2 are listed, and if the maximum range values 3, 4, and 5 are listed, the following ranges are all expected: 1-3, 1-4, 1-5, 2- 3, 2-4 and 2-5.
  • the numerical range "a-b” represents an abbreviated representation of any combination of real numbers between a and b, where a and b are both real numbers.
  • the numerical range "0-5" indicates that all real numbers between "0-5" have been listed in this article, and "0-5" is only an abbreviated representation of the combination of these values.
  • a certain parameter is an integer ⁇ 2
  • the method includes steps (a) and (b), which means that the method may include steps (a) and (b) performed in sequence, and may also include steps (b) and (a) performed in sequence.
  • steps (c) means that step (c) may be added to the method in any order, for example, the method may include steps (a), (b) and (c) , may also include steps (a), (c) and (b), may also include steps (c), (a) and (b) and so on.
  • the “comprising” and “comprising” mentioned in this application mean open or closed.
  • the “comprising” and “comprising” may mean that other components not listed may be included or included, or only listed components may be included or included.
  • the term "or” is inclusive unless otherwise stated.
  • the phrase "A or B” means “A, B, or both A and B.” More specifically, the condition "A or B” is satisfied by either of the following: A is true (or exists) and B is false (or does not exist); A is false (or does not exist) and B is true (or exists) ; or both A and B are true (or exist).
  • the median particle diameter Dv 50 refers to the particle diameter corresponding to when the cumulative volume distribution percentage of the positive electrode active material reaches 50%.
  • the median diameter Dv 50 of the positive electrode active material can be measured by laser diffraction particle size analysis.
  • a laser particle size analyzer such as Malvern Master Size 3000 is used for measurement.
  • coating layer refers to a material layer coated on the inner core.
  • the material layer can completely or partially cover the inner core.
  • the use of “coating layer” is only for the convenience of description and is not intended to limit the present invention. invention.
  • thickness of the coating layer refers to the thickness of the material layer coated on the inner core in the radial direction of the inner core.
  • the term “source” refers to a compound that is the source of a certain element.
  • the types of the “source” include but are not limited to carbonates, sulfates, nitrates, elemental substances, halides, oxides and hydroxide etc.
  • the inventors of the present application have found in practical work that the manganese elution is relatively serious in the deep charge and discharge process of the lithium manganese phosphate positive electrode active material. Although there are attempts in the prior art to coat lithium manganese phosphate with lithium iron phosphate to reduce interfacial side reactions, this coating cannot prevent the migration of dissolved manganese into the electrolyte. The dissolved manganese is reduced to metal manganese after migrating to the negative electrode.
  • the metal manganese produced is equivalent to a "catalyst", which can catalyze the decomposition of the SEI film (solid electrolyte interphase, solid electrolyte interphase film) on the surface of the negative electrode, and part of the by-products produced are gases, which can easily cause the battery to expand and affect the safety of the secondary battery.
  • the other part is deposited on the surface of the negative electrode, hindering the passage of lithium ions into and out of the negative electrode, causing the impedance of the secondary battery to increase and affecting the kinetic performance of the battery.
  • the electrolyte and the active lithium inside the battery are continuously consumed, which has an irreversible impact on the capacity retention of the secondary battery.
  • the inventors found that for lithium manganese phosphate positive electrode active materials, the problems of severe manganese dissolution and high surface reactivity may be caused by the ginger-Taylor effect of Mn 3+ and the change of Li + channel size after delithiation. For this reason, the inventor obtained a positive electrode active material that can significantly reduce manganese dissolution and lattice change rate by modifying lithium manganese phosphate, and then has good cycle performance, high-temperature storage performance and safety performance.
  • a first aspect of the present application provides a positive electrode active material with a core-shell structure, which includes an inner core and a shell covering the inner core,
  • the shell includes a first cladding layer covering the inner core and a second cladding layer covering the first cladding layer,
  • the first cladding layer includes pyrophosphate MP 2 O 7 and phosphate XPO 4 , wherein the M and X are each independently selected from Li, Fe, Ni, Mg, Co, Cu, Zn, Ti, One or more of Ag, Zr, Nb or Al;
  • the second cladding layer includes carbon.
  • the above-mentioned limitation on the numerical range of y is not only a limitation on the stoichiometric number of each element as A, but also a limitation on each element as A.
  • Limitation of the sum of stoichiometric numbers For example, when A is two or more elements A1, A2...An, the stoichiometric numbers y1, y2...yn of A1, A2...An each need to fall within the numerical range defined by the application for y, and y1 The sum of , y2 ... yn also needs to fall within this value range.
  • the limitation of the numerical range of the stoichiometric number of R in this application also has the above meaning.
  • the lithium manganese phosphate positive electrode active material of the present application has a core-shell structure with two cladding layers, wherein the inner core includes Li 1+x Mn 1-y A y P 1-z R z O 4 .
  • the element A doped at the manganese position of lithium manganese phosphate in the inner core helps to reduce the lattice change rate of lithium manganese phosphate during lithium deintercalation, improves the structural stability of lithium manganese phosphate cathode material, and greatly reduces the dissolution of manganese And reduce the oxygen activity on the particle surface.
  • the element R doped at the phosphorus site helps to change the difficulty of the change of the Mn-O bond length, thereby reducing the migration barrier of lithium ions, promoting the migration of lithium ions, and improving the rate performance of the secondary battery.
  • the first coating layer of the positive electrode active material of the present application includes pyrophosphate and phosphate. Due to the high migration barrier (>1eV) of transition metals in pyrophosphate, the dissolution of transition metals can be effectively suppressed. Phosphate has an excellent ability to conduct lithium ions, and can reduce the content of lithium impurities on the surface.
  • the second cladding layer is a carbon-containing layer, it can effectively improve the electrical conductivity and desolvation ability of LiMnPO 4 .
  • the "barrier" effect of the second cladding layer can further hinder the migration of manganese ions into the electrolyte and reduce the corrosion of the active materials by the electrolyte.
  • this application can effectively suppress the dissolution of Mn in the process of lithium intercalation and deintercalation, and at the same time promote the migration of lithium ions, thereby improving the rate performance of the battery cell and increasing the secondary The cycle performance and high temperature performance of the battery.
  • the positive electrode active material of the present application is basically consistent with the positions of the main characteristic peaks before doping of LiMnPO, indicating that doping
  • the mixed lithium manganese phosphate positive electrode active material has no impurity phase, and the improvement of the performance of the secondary battery is mainly caused by element doping, not the impurity phase.
  • the interplanar spacing of the phosphate of the first cladding layer is 0.345-0.358nm, and the included angle of the crystal direction (111) is 24.25°-26.45°; the first cladding layer The interplanar distance of pyrophosphate is 0.293-0.326nm, and the included angle of crystal direction (111) is 26.41°-32.57°.
  • the impurity phase in the cladding layer can be effectively avoided, thereby increasing the gram capacity of the material, and cycle performance and rate performance.
  • the ratio of y to 1-y is 1:10 to 10:1, optionally 1:4 to 1:1.
  • y represents the sum of stoichiometric numbers of Mn-site doping elements.
  • the ratio of z to 1-z is 1:9 to 1:999, optionally 1:499 to 1:249.
  • y represents the sum of the stoichiometric numbers of the P-site doping elements.
  • the coating amount of the first coating layer is greater than 0% by weight and less than or equal to 7% by weight, optionally 4-5.6% by weight, based on the weight of the inner core.
  • the coating amount of the first coating layer is within the above range, the dissolution of manganese can be further suppressed, and at the same time, the transport of lithium ions can be further promoted. And it can effectively avoid the following situation: if the coating amount of the first coating layer is too small, it may cause insufficient inhibition of pyrophosphate on manganese dissolution, and the improvement of lithium ion transport performance is not significant; If the coating amount of the first coating layer is too large, the coating layer may be too thick, which increases the battery impedance and affects the kinetic performance of the battery.
  • the weight ratio of pyrophosphate to phosphate in the first coating layer is 1:3 to 3:1, optionally 1:3 to 1:1.
  • the proper ratio of pyrophosphate and phosphate is conducive to giving full play to the synergistic effect of the two. And it can effectively avoid the following situations: if there is too much pyrophosphate and too little phosphate, it may lead to an increase in battery impedance; if there is too much phosphate and too little pyrophosphate, the effect of inhibiting the dissolution of manganese is not significant.
  • the crystallinity of the pyrophosphate salt and the phosphate salt is each independently 10% to 100%, optionally 50% to 100%.
  • pyrophosphate and phosphate with a certain degree of crystallinity are beneficial to keep the structure of the first coating layer stable and reduce lattice defects. On the one hand, this is beneficial to give full play to the role of pyrophosphate in hindering the dissolution of manganese. On the other hand, it is also beneficial to phosphate to reduce the content of lithium on the surface and the valence state of oxygen on the surface, thereby reducing the interface side reactions between the positive electrode material and the electrolyte, and reducing the The consumption of electrolyte improves the cycle performance and safety performance of the battery.
  • the crystallinity of pyrophosphate and phosphate can be adjusted, for example, by adjusting the process conditions of the sintering process, such as sintering temperature, sintering time, and the like.
  • the crystallinity of pyrophosphate and phosphate salts can be measured by methods known in the art, such as by X-ray diffraction, densitometry, infrared spectroscopy, differential scanning calorimetry, and nuclear magnetic resonance absorption methods.
  • the coating amount of the second coating layer is greater than 0% by weight and less than or equal to 6% by weight, optionally 3-5% by weight, based on the weight of the inner core.
  • the carbon-containing layer as the second coating layer can play a "barrier" function to avoid direct contact between the positive electrode active material and the electrolyte, thereby reducing the corrosion of the active material by the electrolyte and improving the safety performance of the battery at high temperatures.
  • it has strong electrical conductivity, which can reduce the internal resistance of the battery, thereby improving the kinetic performance of the battery.
  • the gram capacity of the carbon material is low, when the amount of the second coating layer is too large, the gram capacity of the entire positive electrode active material may be reduced. Therefore, when the coating amount of the second coating layer is in the above range, the kinetic performance and safety performance of the battery can be further improved without sacrificing the gram capacity of the positive electrode active material.
  • the A is selected from at least two of Fe, Ti, V, Ni, Co and Mg.
  • Simultaneously doping two or more of the above-mentioned elements on the manganese site in the lithium manganese phosphate positive electrode active material is beneficial to enhance the doping effect, on the one hand, further reduce the lattice change rate, thereby inhibiting the dissolution of manganese, and reducing the electrolyte and active lithium. On the other hand, it is also beneficial to further reduce the surface oxygen activity and reduce the interface side reaction between the positive electrode active material and the electrolyte, thereby improving the cycle performance and high temperature storage performance of the battery.
  • the Li/Mn antisite defect concentration of the positive electrode active material is less than 4%, optionally less than 2%.
  • the Li/Mn antisite defect means that in the LiMnPO 4 lattice, the positions of Li + and Mn 2+ are exchanged. Since the Li + transport channel is a one-dimensional channel, Mn 2+ is difficult to migrate in the Li + transport channel, so the Mn 2+ with antisite defects will hinder the transport of Li + .
  • the gram capacity and rate performance of LiMnPO4 can be improved by controlling the Li/Mn antisite defect concentration at a low level.
  • the antisite defect concentration can be measured according to JIS K 0131-1996, for example.
  • the lattice change rate of the positive electrode active material is less than 6%, optionally less than 4%.
  • the lithium-deintercalation process of LiMnPO 4 is a two-phase reaction.
  • the interfacial stress of the two phases is determined by the lattice change rate. The smaller the lattice change rate, the smaller the interfacial stress and the easier Li + transport. Therefore, reducing the lattice change rate of the inner core will be beneficial to enhance the Li + transport ability, thereby improving the rate performance of secondary batteries.
  • the average discharge voltage of the positive electrode active material is above 3.5V, and the discharge gram capacity is above 140mAh/g; optionally, the average discharge voltage is above 3.6V, and the discharge gram capacity is above 145mAh /g or more.
  • the average discharge voltage of undoped LiMnPO 4 is above 4.0V, its discharge gram capacity is low, usually less than 120mAh/g, so the energy density is low; adjusting the lattice change rate by doping can make it The discharge gram capacity has been greatly improved, and the overall energy density has increased significantly under the condition of a slight drop in the average discharge voltage.
  • the surface oxygen valence state of the positive electrode active material is below -1.88, optionally between -1.98 and -1.88.
  • the higher the valence state of oxygen in the compound the stronger its ability to obtain electrons, that is, the stronger the oxidation.
  • the reactivity of the surface of the positive electrode material can be reduced, and the interface side reaction between the positive electrode material and the electrolyte can be reduced, thereby improving the secondary The cycle performance and high temperature storage performance of the battery.
  • the positive electrode active material has a compacted density at 3 tons (T) of 2.0 g/cm 3 or more, optionally 2.2 g/cm 3 or more.
  • the compacted density can be measured according to GB/T 24533-2009, for example.
  • the second aspect of the present application provides the preparation method of the positive electrode active material of the first aspect of the present application, which comprises the following steps:
  • the Said A is selected from one or more of Zn, Al, Na, K, Mg, Mo, W, Ti, V, Zr, Fe, Ni, Co, Ga, Sn, Sb, Nb and Ge, and may be One or more of Fe, Ti, V, Ni, Co and Mg
  • the R is selected from one or more of B, Si, N and S;
  • Coating step provide MP 2 O 7 powder and XPO 4 suspension containing carbon source, add the core material, MP 2 O 7 powder into XPO 4 suspension containing carbon source and mix, Sintering to obtain a positive electrode active material, wherein the M and X are each independently selected from one or more of Li, Fe, Ni, Mg, Co, Cu, Zn, Ti, Ag, Zr, Nb or Al;
  • the positive electrode active material has a core-shell structure, which includes an inner core and a shell covering the inner core, and the shell includes a first cladding layer covering the inner core and a shell covering the first cladding layer.
  • the second coating layer, the first coating layer includes pyrophosphate MP 2 O 7 and phosphate XPO 4 , and the second coating layer includes carbon.
  • the preparation method of the present application has no special limitation on the source of the material.
  • the core material in the preparation method of the present application may be commercially available, or prepared by the method of the present application.
  • the core material is prepared by the method described below.
  • the step of providing the core material comprises the following steps:
  • Step (1) mixing and stirring a source of manganese, a source of element A, and an acid in a container to obtain manganese salt particles doped with element A;
  • the step (1) is carried out at a temperature of 20-120°C, optionally 25-80°C; and/or,
  • the stirring in the step (1) is carried out at 500-700 rpm for 60-420 minutes, optionally for 120-360 minutes.
  • the doping elements By controlling the reaction temperature, stirring rate and mixing time during doping, the doping elements can be evenly distributed, the lattice defects can be reduced, the dissolution of manganese can be suppressed, and the interface side reaction between the positive electrode active material and the electrolyte can be reduced, thereby improving the grammage of the material. capacity and rate performance, etc.
  • the source of a certain element may include one or more of elemental elements, sulfates, halides, nitrates, organic acid salts, oxides or hydroxides of the element.
  • the body is the source that can realize the purpose of the preparation method of the present application.
  • the source of the element A is selected from one or more of element A, sulfate, halide, nitrate, organic acid salt, oxide or hydroxide; and/or, the element
  • the source of R is selected from one or more of elemental R elements, sulfates, halides, nitrates, organic acid salts, oxides or hydroxides, and inorganic acids of element R.
  • the source of manganese in the present application is one or more selected from elemental manganese, manganese dioxide, manganese phosphate, manganese oxalate, and manganese carbonate.
  • element A is iron
  • the source of iron is one or more selected from ferrous carbonate, ferric hydroxide, and ferrous sulfate.
  • the acid is selected from one or more of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, organic acids such as oxalic acid, etc., and may be oxalic acid.
  • the acid is a dilute acid having a concentration of 60% by weight or less.
  • the mineral acid of element R is selected from one or more of phosphoric acid, nitric acid, boric acid, silicic acid, ortho silicic acid.
  • the source of lithium in the present application is one or more selected from lithium carbonate, lithium hydroxide, lithium phosphate, and lithium dihydrogen phosphate.
  • the source of phosphorus in the present application is one or more selected from diammonium hydrogen phosphate, ammonium dihydrogen phosphate, ammonium phosphate and phosphoric acid.
  • the source of carbon in the present application is an organic carbon source, and the organic carbon source is selected from one of starch, sucrose, glucose, polyvinyl alcohol, polyethylene glycol, and citric acid. one or more species.
  • the solvent used in the preparation method described in the present application is a solvent commonly used in the art.
  • the solvents in the preparation method of the present application can be independently selected from at least one of ethanol and water (eg, deionized water).
  • the pH of the solution is controlled to be 4-6. It should be noted that in this application, the pH of the resulting mixture can be adjusted by methods commonly used in the art, for example, by adding acid or base.
  • step (2) the molar ratio of the manganese salt particles to the source of lithium and the source of phosphorus is 1:0.5-2.1:0.5-2.1.
  • the sintering condition is: sintering at 600-800° C. for 4-10 hours in an atmosphere of inert gas or a mixture of inert gas and hydrogen.
  • the mixture of inert gas and hydrogen is nitrogen (70-90 volume %)+hydrogen (10-30 volume %).
  • the MP 2 O 7 powder is a commercially available product, or alternatively, the MP 2 O 7 powder is prepared by adding a source of element M and a source of phosphorus to In the solvent, the mixture is obtained, the pH of the mixture is adjusted to 4-6, stirred and fully reacted, then obtained by drying and sintering, wherein M is selected from Li, Fe, Ni, Mg, Co, Cu, Zn, Ti, Ag, Zr , Nb or Al in one or more.
  • the drying step is drying at 100-300°C, optionally 150-200°C, for 4-8h.
  • the sintering step is sintering at 500-800° C., optionally 650-800° C., in an inert gas atmosphere for 4-10 hours.
  • the XPO suspension comprising a source of carbon is commercially available, or alternatively, is prepared by combining a source of lithium, a source of X, phosphorus The source of carbon and the source of carbon are uniformly mixed in a solvent, and then the reaction mixture is heated to 60-120° C. for 2-8 hours to obtain the XPO 4 suspension containing the source of carbon.
  • the pH of the mixture is adjusted to 4-6.
  • the mass ratio of the lithium manganese phosphate doped with the A element and the R element, MP 2 O 7 powder and XPO 4 suspension containing carbon source It is: 1:(0.001-0.05):(0.001-0.05).
  • the sintering temperature is 500-800° C., and the sintering time is 4-10 h.
  • the median particle diameter Dv50 of the primary particles of the double-layer coated lithium manganese phosphate positive electrode active material of the present application is 50-2000 nm.
  • the third aspect of the present application provides a positive electrode sheet, which includes a positive electrode current collector and a positive electrode film layer arranged on at least one surface of the positive electrode current collector, and the positive electrode film layer includes the lithium manganese phosphate positive electrode active material according to the first aspect of the present application Or the lithium manganese phosphate positive electrode active material prepared according to the method of the second aspect of the present application, and the content of the positive electrode active material in the positive electrode film layer is more than 10% by weight, based on the total weight of the positive electrode film layer.
  • the content of the positive electrode active material in the positive electrode film layer is 90-99.5% by weight, based on the total weight of the positive electrode film layer.
  • the positive electrode current collector has two opposing surfaces in its own thickness direction, and the positive electrode film layer is disposed on any one or both of the two opposing surfaces of the positive electrode current collector.
  • the positive electrode current collector can be a metal foil or a composite current collector.
  • aluminum foil can be used as the metal foil.
  • the composite current collector may include a polymer material base and a metal layer formed on at least one surface of the polymer material base.
  • the composite current collector can be formed by forming metal materials (aluminum, aluminum alloy, nickel, nickel alloy, titanium, titanium alloy, silver and silver alloy, etc.) on a polymer material substrate (such as polypropylene (PP), polyethylene terephthalic acid Formed on substrates such as ethylene glycol ester (PET), polybutylene terephthalate (PBT), polystyrene (PS), polyethylene (PE), etc.).
  • PP polypropylene
  • PET ethylene glycol ester
  • PBT polybutylene terephthalate
  • PS polystyrene
  • PE polyethylene
  • the positive electrode film layer may further optionally include a binder.
  • the binder may include polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), vinylidene fluoride-tetrafluoroethylene-propylene terpolymer, vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene At least one of ethylene terpolymer, tetrafluoroethylene-hexafluoropropylene copolymer and fluorine-containing acrylate resin.
  • the positive electrode film layer may also optionally include a conductive agent.
  • the conductive agent may include at least one of superconducting carbon, acetylene black, carbon black, Ketjen black, carbon dots, carbon nanotubes, graphene, and carbon nanofibers.
  • the positive electrode film layer of the present application includes 90-99.5% of the lithium manganese phosphate positive electrode active material of the first aspect of the present application, 0.4-5.5% of the binder, 0.1-2.5% of the conductive carbon and 0.001- 1% of other additives, based on the total weight of the positive film layer.
  • the positive electrode film layer of the present application may also include other additives such as dispersants, wetting agents, rheology modifiers and other additives commonly used in this field.
  • the positive electrode sheet can be prepared in the following manner: the above-mentioned components used to prepare the positive electrode sheet, such as positive electrode active material, conductive agent, binder and any other components, are dispersed in a solvent (such as N -methylpyrrolidone) to form a positive electrode slurry; the positive electrode slurry is coated on the positive electrode current collector, and after drying, cold pressing and other processes, the positive electrode sheet can be obtained.
  • a solvent such as N -methylpyrrolidone
  • the coating weight of the anode film layer of the present application is 0.28-0.45g/1540.25mm 2 , and the compacted density reaches 2.2-2.8g/cm 3 .
  • the negative electrode sheet includes a negative electrode current collector and a negative electrode film layer arranged on at least one surface of the negative electrode current collector, and the negative electrode film layer includes a negative electrode active material.
  • the negative electrode current collector has two opposing surfaces in its own thickness direction, and the negative electrode film layer is disposed on any one or both of the two opposing surfaces of the negative electrode current collector.
  • the negative electrode current collector can use a metal foil or a composite current collector.
  • copper foil can be used as the metal foil.
  • the composite current collector may include a base layer of polymer material and a metal layer formed on at least one surface of the base material of polymer material.
  • Composite current collectors can be formed by metal materials (copper, copper alloys, nickel, nickel alloys, titanium, titanium alloys, silver and silver alloys, etc.) on polymer material substrates (such as polypropylene (PP), polyethylene terephthalic acid It is formed on substrates such as ethylene glycol ester (PET), polybutylene terephthalate (PBT), polystyrene (PS), polyethylene (PE), etc.).
  • the negative electrode active material can be a negative electrode active material known in the art for batteries.
  • the negative electrode active material may include at least one of the following materials: artificial graphite, natural graphite, soft carbon, hard carbon, silicon-based material, tin-based material, lithium titanate, and the like.
  • the silicon-based material may be selected from at least one of elemental silicon, silicon-oxygen compounds, silicon-carbon composites, silicon-nitrogen composites, and silicon alloys.
  • the tin-based material may be selected from at least one of simple tin, tin oxide compounds and tin alloys.
  • the present application is not limited to these materials, and other conventional materials that can be used as negative electrode active materials of batteries can also be used. These negative electrode active materials may be used alone or in combination of two or more.
  • the negative electrode film layer may further optionally include a binder.
  • the binder can be selected from styrene-butadiene rubber (SBR), polyacrylic acid (PAA), sodium polyacrylate (PAAS), polyacrylamide (PAM), polyvinyl alcohol (PVA), sodium alginate (SA), poly At least one of methacrylic acid (PMAA) and carboxymethyl chitosan (CMCS).
  • the negative electrode film layer may also optionally include a conductive agent.
  • the conductive agent can be selected from at least one of superconducting carbon, acetylene black, carbon black, Ketjen black, carbon dots, carbon nanotubes, graphene and carbon nanofibers.
  • the negative electrode film layer may optionally include other additives, such as thickeners (such as sodium carboxymethylcellulose (CMC-Na)) and the like.
  • thickeners such as sodium carboxymethylcellulose (CMC-Na)
  • CMC-Na sodium carboxymethylcellulose
  • the negative electrode sheet can be prepared in the following manner: the above-mentioned components used to prepare the negative electrode sheet, such as negative electrode active material, conductive agent, binder and any other components, are dispersed in a solvent (such as deionized water) to form a negative electrode slurry; the negative electrode slurry is coated on the negative electrode current collector, and after drying, cold pressing and other processes, the negative electrode sheet can be obtained.
  • a solvent such as deionized water
  • the electrolyte plays the role of conducting ions between the positive pole piece and the negative pole piece.
  • the present application has no specific limitation on the type of electrolyte, which can be selected according to requirements.
  • electrolytes can be liquid, gel or all solid.
  • the electrolyte is an electrolytic solution.
  • the electrolyte solution includes an electrolyte salt and a solvent.
  • the electrolyte salt may be selected from lithium hexafluorophosphate, lithium tetrafluoroborate, lithium perchlorate, lithium hexafluoroarsenate, lithium bisfluorosulfonyl imide, lithium bistrifluoromethanesulfonyl imide, trifluoromethane At least one of lithium sulfonate, lithium difluorophosphate, lithium difluorooxalate borate, lithium difluorooxalate borate, lithium difluorodifluorooxalatephosphate and lithium tetrafluorooxalatephosphate.
  • the solvent may be selected from ethylene carbonate, propylene carbonate, ethyl methyl carbonate, diethyl carbonate, dimethyl carbonate, dipropyl carbonate, methyl propyl carbonate, ethyl propyl carbonate, Butylene carbonate, fluoroethylene carbonate, methyl formate, methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, propyl propionate, methyl butyrate, ethyl butyrate At least one of ester, 1,4-butyrolactone, sulfolane, dimethyl sulfone, methyl ethyl sulfone and diethyl sulfone.
  • the electrolyte may optionally include additives.
  • additives may include negative electrode film-forming additives, positive electrode film-forming additives, and additives that can improve certain performances of the battery, such as additives that improve battery overcharge performance, additives that improve high-temperature or low-temperature performance of batteries, and the like.
  • a separator is further included in the secondary battery.
  • the present application has no particular limitation on the type of the isolation membrane, and any known porous structure isolation membrane with good chemical stability and mechanical stability can be selected.
  • the material of the isolation film can be selected from at least one of glass fiber, non-woven fabric, polyethylene, polypropylene and polyvinylidene fluoride.
  • the separator can be a single-layer film or a multi-layer composite film, without any particular limitation. When the separator is a multilayer composite film, the materials of each layer may be the same or different, and there is no particular limitation.
  • the positive pole piece, the negative pole piece and the separator can be made into an electrode assembly through a winding process or a lamination process.
  • the fourth aspect of the application provides a secondary battery, which includes the positive electrode active material described in the first aspect of the application or the positive electrode active material prepared by the method described in the second aspect of the application or the positive electrode active material described in the third aspect of the application Positive pole piece.
  • a secondary battery typically includes a positive pole piece, a negative pole piece, an electrolyte, and a separator.
  • active ions are intercalated and extracted back and forth between the positive electrode and the negative electrode.
  • the electrolyte plays the role of conducting ions between the positive pole piece and the negative pole piece.
  • the separator is arranged between the positive pole piece and the negative pole piece, which mainly plays a role in preventing the short circuit of the positive and negative poles, and at the same time allows ions to pass through.
  • a lithium ion secondary battery may include an outer package.
  • the outer package can be used to package the above-mentioned electrode assembly and electrolyte.
  • the outer package of the lithium-ion secondary battery may be a hard case, such as a hard plastic case, aluminum case, steel case, and the like.
  • the outer packaging of the lithium-ion secondary battery may also be a soft bag, such as a pouch-type soft bag.
  • the material of the soft bag may be plastic, and examples of plastic include polypropylene (PP), polybutylene terephthalate (PBT), and polybutylene succinate (PBS).
  • FIG. 3 shows a square-shaped secondary battery 5 as an example.
  • the outer package may include a housing 51 and a cover 53 .
  • the housing 51 may include a bottom plate and a side plate connected to the bottom plate, and the bottom plate and the side plates enclose to form an accommodating cavity.
  • the housing 51 has an opening communicating with the accommodating cavity, and the cover plate 53 can cover the opening to close the accommodating cavity.
  • the positive pole piece, the negative pole piece and the separator can be formed into an electrode assembly 52 through a winding process or a lamination process.
  • the electrode assembly 52 is packaged in the accommodating cavity. Electrolyte is infiltrated in the electrode assembly 52 .
  • the number of electrode assemblies 52 contained in the secondary battery 5 can be one or more, and those skilled in the art can select according to specific actual needs.
  • the lithium-ion secondary battery can be assembled into a battery module, and the number of lithium-ion batteries contained in the battery module can be one or more, and the specific number can be selected by those skilled in the art according to the application and capacity of the battery module.
  • FIG. 5 is a battery module 4 as an example.
  • a plurality of lithium-ion batteries 5 can be arranged sequentially along the length direction of the battery module 4 .
  • the plurality of lithium ion batteries 5 can be fixed by fasteners.
  • the battery module 4 may also include a housing with an accommodating space, and a plurality of lithium-ion batteries 5 are accommodated in the accommodating space.
  • the above-mentioned battery modules can also be assembled into a battery pack, and the number of battery modules contained in the battery pack can be one or more, and the specific number can be selected by those skilled in the art according to the application and capacity of the battery pack.
  • the battery pack 1 may include a battery box and a plurality of battery modules 4 disposed in the battery box.
  • the battery box includes an upper box body 2 and a lower box body 3 , the upper box body 2 can cover the lower box body 3 and form a closed space for accommodating the battery module 4 .
  • Multiple battery modules 4 can be arranged in the battery box in any manner.
  • the present application also provides an electric device, which includes at least one of the secondary battery, battery module, or battery pack provided in the present application.
  • the secondary battery, battery module, or battery pack can be used as a power source of the electric device, and can also be used as an energy storage unit of the electric device.
  • the electric devices may include mobile devices (such as mobile phones, notebook computers, etc.), electric vehicles (such as pure electric vehicles, hybrid electric vehicles, plug-in hybrid electric vehicles, electric bicycles, electric scooters, electric golf carts, etc.) , electric trucks, etc.), electric trains, ships and satellites, energy storage systems, etc., but not limited thereto.
  • a secondary battery, a battery module or a battery pack can be selected according to its use requirements.
  • FIG. 8 is an example of an electrical device.
  • the electric device is a pure electric vehicle, a hybrid electric vehicle, or a plug-in hybrid electric vehicle.
  • a battery pack or a battery module may be used.
  • a device may be a cell phone, tablet, laptop, or the like.
  • the device is generally required to be light and thin, and a secondary battery can be used as a power source.
  • the reactor was heated to 80° C. and stirred at 600 rpm for 6 hours until the reaction was terminated (no bubbles were generated), and a Fe, Co, V and S co-doped manganese oxalate suspension was obtained. Then the suspension was filtered, the filter cake was dried at 120° C., and then ground to obtain Fe, Co and V co-doped manganese oxalate dihydrate particles with a median diameter Dv50 of 100 nm.
  • the drying temperature was set at 250° C. and dried for 4 hours to obtain a powder.
  • a protective atmosphere of nitrogen (90 volume %) + hydrogen (10 volume %) the above powder was sintered at 700° C. for 4 hours to obtain 1572.1 g of Fe, Co, V and S co-doped lithium manganese phosphate.
  • lithium iron pyrophosphate powder 4.77 g of lithium carbonate, 7.47 g of ferrous carbonate, 14.84 g of ammonium dihydrogen phosphate and 1.3 g of oxalic acid dihydrate were dissolved in 50 ml of deionized water. The pH of the mixture was 5, and the reaction mixture was stirred for 2 hours to fully react. Then the temperature of the reacted solution was raised to 80°C and maintained at this temperature for 4 hours to obtain a suspension containing Li 2 FeP 2 O 7 , which was filtered, washed with deionized water, and dried at 120°C for 4 hours , to obtain powder. The powder was sintered at 650° C. under a nitrogen atmosphere for 8 hours, cooled naturally to room temperature, and then ground to obtain Li 2 FeP 2 O 7 powder.
  • lithium iron phosphate suspension dissolve 11.1g of lithium carbonate, 34.8g of ferrous carbonate, 34.5g of ammonium dihydrogen phosphate, 1.3g of oxalic acid dihydrate and 74.6g of sucrose (calculated as C 12 H 22 O 11 , the same below) The mixture was obtained in 150 ml of deionized water, and then stirred for 6 hours to fully react the above mixture. The reacted solution was then warmed up to 120 °C and kept at this temperature for 6 hours to obtain a suspension containing LiFePO4 .
  • the above-mentioned double-coated lithium manganese phosphate positive electrode active material, conductive agent acetylene black, and binder polyvinylidene fluoride (PVDF) were added to N-methylpyrrolidone (NMP) in a weight ratio of 92:2.5:5.5 ), stir and mix evenly to obtain positive electrode slurry. Then, the positive electrode slurry was uniformly coated on the aluminum foil at a thickness of 0.280g/1540.25mm 2 , dried, cold pressed, and cut to obtain the positive electrode sheet.
  • NMP N-methylpyrrolidone
  • Negative electrode active material artificial graphite, hard carbon, conductive agent acetylene black, binder styrene-butadiene rubber (SBR), thickener carboxymethylcellulose sodium (CMC-Na) are 90: 5: 2: 2 according to weight ratio : 1 dissolved in deionized water as a solvent, stirred and mixed evenly to prepare negative electrode slurry.
  • the negative electrode slurry was evenly coated on the copper foil of the negative electrode current collector at a ratio of 0.117g/1540.25mm 2 , and the negative electrode sheet was obtained by drying, cold pressing, and slitting.
  • a commercially available PP-PE copolymer microporous film with a thickness of 20 ⁇ m and an average pore diameter of 80 nm was used.
  • the above obtained positive electrode sheet, separator, and negative electrode sheet are stacked in order, so that the separator is in the middle of the positive and negative electrodes to play the role of isolation, and the bare cell is obtained by winding. Place the bare cell in the outer package, inject the above electrolyte and package it to obtain a full battery (hereinafter also referred to as "full battery").
  • the above-mentioned double-coated lithium manganese phosphate positive electrode active material, PVDF, and acetylene black were added to NMP at a weight ratio of 90:5:5, and stirred in a drying room to form a slurry.
  • the above slurry is coated on the aluminum foil, dried and cold pressed to form a positive electrode sheet.
  • the coating amount was 0.2 g/cm 2
  • the compacted density was 2.0 g/cm 3 .
  • a lithium sheet is used as the negative electrode, and a solution of 1 mol/L LiPF 6 in ethylene carbonate (EC) + diethyl carbonate (DEC) + dimethyl carbonate (DMC) with a volume ratio of 1:1:1 is used as the electrolytic solution.
  • liquid and assembled into a button battery (hereinafter also referred to as "button battery") in a button box together with the above-mentioned positive pole piece prepared.
  • Examples 1-15 were the same as those of Examples 1-14.
  • Example 1-17 Except that in Example 1-16, 466.4g of NiCO 3 , 5.0g of zinc carbonate and 7.2g of titanium sulfate were used instead of ferrous carbonate during the preparation of the co-doped lithium manganese phosphate core, and in Example 1-17
  • the ferrous carbonate of 455.2g and the vanadium dichloride of 8.5g are used in the preparation process of the lithium manganese phosphate inner core, and the ferrous carbonate of 455.2g is used in the preparation process of the co-doped lithium manganese phosphate inner core in embodiment 1-18 , 4.9g of vanadium dichloride and 2.5g of magnesium carbonate, the conditions of Examples 1-17 to 1-19 are the same as in Example 1-7.
  • embodiment 1-19 uses the lithium carbonate of 369.4g in the preparation process of co-doped lithium manganese phosphate inner core, and replaces dilute sulfuric acid with the dilute nitric acid of 60% concentration of 1.05g
  • embodiment 1-20 is in co-doped
  • the conditions of Examples 1-19 to 1-20 are the same as those of Example 1-18, except that 369.7 g of lithium carbonate and 0.78 g of silicic acid are used instead of dilute sulfuric acid during the preparation of the lithium manganese phosphate inner core.
  • Examples 1-21 632.0g of manganese carbonate, 463.30g of ferrous carbonate, 30.5g of vanadium dichloride, 21.0g of magnesium carbonate and 0.78g of silicate were used in the preparation process of the co-doped lithium manganese phosphate core.
  • Embodiment 1-22 uses 746.9g manganese carbonate, 289.6g ferrous carbonate, 60.9g of vanadium dichloride, 42.1g of magnesium carbonate and 0.78g of silicate in the preparation process of co-doped lithium manganese phosphate core
  • the conditions of Examples 1-21 to 1-22 are the same as those of Example 1-20.
  • embodiment 1-23 uses 804.6g manganese carbonate, 231.7g ferrous carbonate, 1156.2g ammonium dihydrogen phosphate, 1.2g boric acid (mass fraction 99.5%) and 370.8 g lithium carbonate; embodiment 1-24 uses 862.1g manganese carbonate, 173.8g ferrous carbonate, 1155.1g ammonium dihydrogen phosphate, boric acid (mass fraction 99.5% of 1.86g) in the preparation process of co-doped lithium manganese phosphate core ) and 371.6g lithium carbonate, the conditions of embodiment 1-23 to 1-24 are identical with embodiment 1-22.
  • embodiment 1-25 uses 370.1g of lithium carbonate, 1.56g of silicic acid and 1147.7g of ammonium dihydrogen phosphate in the preparation process of the co-doped lithium manganese phosphate core, the conditions of embodiment 1-25 and embodiment 1-20 are the same.
  • embodiment 1-26 uses 368.3g lithium carbonate, 4.9g mass fraction to be 60% dilute sulfuric acid, 919.6g manganese carbonate, 224.8g ferrous carbonate, 3.7g dichloro Except the ammonium dihydrogen phosphate of vanadium, 2.5g magnesium carbonate and 1146.8g, the condition of embodiment 1-26 is identical with embodiment 1-20.
  • Example 1-27 uses 367.9g of lithium carbonate, 6.5g concentration of 60% dilute sulfuric acid and 1145.4g of ammonium dihydrogen phosphate in the preparation process of the co-doped lithium manganese phosphate core, the conditions of Example 1-27 Same as Example 1-20.
  • embodiment 1-28 to 1-33 uses 1034.5g manganese carbonate, 108.9g ferrous carbonate, 3.7g vanadium dichloride and 2.5g magnesium carbonate in the preparation process of co-doped lithium manganese phosphate inner core, the use of lithium carbonate
  • the amounts are: 367.6g, 367.2g, 366.8g, 366.4g, 366.0g, and 332.4g
  • the amounts of ammonium dihydrogen phosphate are: 1144.5g, 1143.4g, 1142.2g, 1141.1g, 1139.9g, and 1138.8g
  • Concentration is that the consumption of the dilute sulfuric acid of 60% is respectively: except 8.2g, 9.8g, 11.4g, 13.1g, 14.7g and 16.3g, the conditions of embodiment 1-28 to 1-33 are identical with embodiment 1-20 .
  • the sintering temperature in the powder sintering step is 550°C, and the sintering time is 1h to control the crystallinity of Li 2 FeP 2 O 7 to 30%.
  • the sintering temperature in the coating sintering step is 650° C., and the sintering time is 2 h to control the crystallinity of LiFePO 4 to 30%.
  • Other conditions are the same as in Example 1-1.
  • the sintering temperature in the powder sintering step is 550°C, and the sintering time is 2h to control the crystallinity of Li 2 FeP 2 O 7 to 50%.
  • the sintering temperature in the coating sintering step is 650° C., and the sintering time is 3 h to control the crystallinity of LiFePO 4 to 50%.
  • Other conditions are the same as in Example 1-1.
  • the sintering temperature in the powder sintering step is 600°C, and the sintering time is 3h to control the crystallinity of Li 2 FeP 2 O 7 to 70%.
  • the sintering temperature in the coating sintering step is 650° C., and the sintering time is 4 hours to control the crystallinity of LiFePO 4 to 70%.
  • Other conditions are the same as in Example 1-1.
  • the sintering temperature in the powder sintering step is 650°C, and the sintering time is 4h to control the crystallinity of Li 2 FeP 2 O 7 to 100%.
  • the sintering temperature in the coating sintering step was 700°C, and the sintering time was 6h to control the crystallinity of LiFePO 4 to 100%, other conditions were the same as in Example 1-1.
  • the heating temperature/stirring time in the reactor of Example 3-1 was respectively 60°C/120 minutes; the heating in the reactor of Example 3-2 Temperature/stirring time is respectively 70 °C/120 minutes; The heating temperature/stirring time in embodiment 3-3 reactor is respectively 80 °C/120 minutes; The heating temperature/stirring time in embodiment 3-4 reactor is respectively 90°C/120 minutes; the heating temperature/stirring time in the reactor of Example 3-5 was 100°C/120 minutes respectively; the heating temperature/stirring time in the reactor of Example 3-6 was 110°C/120 minutes respectively; The heating temperature/stirring time in the reactor of embodiment 3-7 is respectively 120 °C/120 minutes; The heating temperature/stirring time in the reactor of embodiment 3-8 is respectively 130 °C/120 minutes; Embodiment 3-9 reaction The heating temperature/stirring time in the kettle is respectively 100 DEG C/60 minutes; The heating temperature/stir
  • Examples 4-1 to 4-4 Except in the preparation process of lithium iron pyrophosphate (Li 2 FeP 2 O 7 ), the drying temperature/drying time in the drying step were 100°C/4h, 150°C/6h, 200°C/6h and 200°C/6h; the sintering temperature and sintering time in the sintering step during the preparation of lithium iron pyrophosphate (Li 2 FeP 2 O 7 ) were 700°C/6h, 700°C/6h, 700°C, respectively Except for °C/6h and 600°C/6h, other conditions are the same as in Examples 1-7.
  • Examples 4-5 to 4-7 Except in the coating process, the drying temperature/drying time in the drying step is 150°C/6h, 150°C/6h and 150°C/6h respectively; Except that the sintering temperature and sintering time in the steps are 600°C/4h, 600°C/6h and 800°C/8h respectively, other conditions are the same as in Examples 1-12.
  • Preparation of carbon-coated lithium manganese phosphate take 1789.6g of manganese oxalate dihydrate particles obtained above, 369.4g of lithium carbonate (calculated as Li 2 CO 3 , the same below), 1150.1g of ammonium dihydrogen phosphate (calculated as NH 4 H 2 PO 4 meter, the same below) and 31 g of sucrose (calculated as C 12 H 22 O 11 , the same below) were added to 20 liters of deionized water, and the mixture was stirred for 10 hours to make it evenly mixed to obtain a slurry. The slurry was transferred to a spray drying device for spray drying and granulation. The drying temperature was set at 250° C. and dried for 4 hours to obtain a powder. In a nitrogen (90 volume %) + hydrogen (10 volume %) protective atmosphere, the above powder was sintered at 700° C. for 4 hours to obtain carbon-coated lithium manganese phosphate.
  • Comparative Example 2 Except for using 689.5g of manganese carbonate and additionally adding 463.3g of ferrous carbonate, other conditions of Comparative Example 2 were the same as those of Comparative Example 1.
  • the powder was sintered at 500°C under a nitrogen atmosphere for 4 hours, and ground after naturally cooling to room temperature.
  • the crystallinity of Li 2 FeP 2 O 7 was controlled to be 5%.
  • Li 2 FeP 2 Except that the consumption of O 7 is 62.8g, other conditions of Comparative Example 5 are the same as Comparative Example 4.
  • lithium iron phosphate suspension 14.7g lithium carbonate, 46.1g ferrous carbonate, 45.8g ammonium dihydrogen phosphate and 50.2g dihydrate oxalic acid were dissolved in 500ml deionized water, then stirred for 6 hours to make The mixture reacted well.
  • the reacted solution is heated to 120°C and maintained at this temperature for 6 hours to obtain a suspension containing LiFePO 4 , and the sintering temperature in the coating sintering step during the preparation of lithium iron phosphate (LiFePO 4 ) is 600°C ,
  • the sintering time is 4h to control the crystallinity of LiFePO 4 to be 8%, when preparing the carbon-coated material, the amount of LiFePO 4 is 62.8g, the other conditions of Comparative Example 6 are the same as Comparative Example 4.
  • lithium iron pyrophosphate powder 2.38 g of lithium carbonate, 7.5 g of ferrous carbonate, 7.4 g of ammonium dihydrogen phosphate and 8.1 g of oxalic acid dihydrate were dissolved in 50 ml of deionized water. The pH of the mixture was 5, and the reaction mixture was stirred for 2 hours to fully react. Then the temperature of the reacted solution was raised to 80°C and maintained at this temperature for 4 hours to obtain a suspension containing Li 2 FeP 2 O 7 , which was filtered, washed with deionized water, and dried at 120°C for 4 hours , to obtain powder. The powder was sintered at 500° C. under a nitrogen atmosphere for 4 hours, cooled naturally to room temperature, and then ground to control the crystallinity of Li 2 FeP 2 O 7 to 5%.
  • lithium iron phosphate suspension 11.1g of lithium carbonate, 34.7g of ferrous carbonate, 34.4g of ammonium dihydrogen phosphate, 37.7g of oxalic acid dihydrate and 37.3g of sucrose (calculated as C 12 H 22 O 11 , the same below) were dissolved in 1500 ml of deionized water, then stirred for 6 hours to fully react the mixture. The reacted solution was then warmed up to 120 °C and kept at this temperature for 6 hours to obtain a suspension containing LiFePO4 .
  • the sintering temperature in the coating sintering step is 600 ° C, and the sintering time is 4 hours to control the LiFePO 4 Except that the crystallinity of 4 was 8%, the other conditions of Comparative Example 7 were the same as those of Comparative Example 4, and amorphous lithium iron pyrophosphate, amorphous lithium iron phosphate, and carbon-coated positive electrode active materials were obtained.
  • the drying temperature/drying time in the drying step was 80°C/3h, 80°C/3h, 80°C/ 3h; the sintering temperature and sintering time in the sintering step during the preparation of lithium iron pyrophosphate (Li 2 FeP 2 O 7 ) were 400°C/3h, 400°C/3h, and 350°C in Comparative Examples 8-10, respectively /2h, the drying temperature/drying time in the drying step during the preparation of lithium iron phosphate (LiFePO 4 ) in Comparative Example 11 was 80°C/3h; and Li 2 FeP 2 O 7 /LiFePO in Comparative Examples 8-11 Except that the dosage of 4 is 47.2g/15.7g, 15.7g/47.2g, 62.8g/0g, 0g/62.8g respectively, other conditions are the same as in Examples 1-7.
  • the button battery prepared above at a constant temperature of 25°C, let it stand for 5 minutes, discharge it at 0.1C to 2.5V, let it stand for 5 minutes, charge it at 0.1C to 4.3V, and then charge it at a constant voltage at 4.3V until the current is less than Equal to 0.05mA, let stand for 5 minutes; then discharge to 2.5V according to 0.1C, the discharge capacity at this time is the initial gram capacity, denoted as D0, the discharge energy is the initial energy, denoted as E0, and the average discharge voltage V after charging is E0 /D0.
  • the above-fabricated full cells were stored at 60°C at 100% state of charge (SOC).
  • SOC state of charge
  • the open circuit voltage (OCV) and AC internal resistance (IMP) of the cell are measured before, after and during storage to monitor the SOC, and the volume of the cell is measured.
  • the full battery was taken out after every 48 hours of storage, and the open circuit voltage (OCV) and internal resistance (IMP) were tested after standing for 1 hour, and the cell volume was measured by the drainage method after cooling to room temperature.
  • the batteries of all the examples kept the SOC above 99% during the experiment until the end of storage.
  • the anode active material sample was prepared as a button charge using the above button charge preparation method, and the above button charge was charged at a small rate of 0.05C until the current was reduced to 0.01C. Then take out the positive pole piece in the button battery, and soak in dimethyl carbonate (DMC) for 8 hours. Then dry, scrape the powder, and screen out the particles whose particle size is less than 500nm. Take a sample and calculate its unit cell volume v1 in the same way as the above-mentioned test fresh sample, and use (v0-v1)/v0 ⁇ 100% as the lattice change rate (unit cell volume change rate) before and after it completely deintercalates lithium. in the table.
  • DMC dimethyl carbonate
  • the Li/Mn antisite defect concentration is obtained. Specifically, import the XRD results tested in the "Measurement Method of Lattice Change Rate” into the General Structural Analysis System (GSAS) software, and automatically obtain the refined results, which include the occupancy of different atoms. By reading the refined As a result, the Li/Mn antisite defect concentration is obtained.
  • GSAS General Structural Analysis System
  • the full battery was discharged to a cut-off voltage of 2.0V at a rate of 0.1C after being cycled at 45°C until the capacity decayed to 80%. Then the battery was disassembled, and the negative pole piece was taken out. On the negative pole piece, 30 discs with a unit area (1540.25mm 2 ) were randomly selected, and the inductively coupled plasma emission spectrum (ICP) was tested with Agilent ICP-OES730. According to the ICP results, the amounts of Fe (if the Mn site of the positive electrode active material is doped with Fe) and Mn are calculated, so as to calculate the dissolution amount of Mn (and Fe doped at the Mn site) after cycling.
  • the test standard is based on EPA-6010D-2014.
  • the positive electrode active material sample prepared above Take 5 g of the positive electrode active material sample prepared above to prepare a button electrode according to the above button electrode preparation method. Charge the button with a small rate of 0.05C until the current decreases to 0.01C. Then take out the positive pole piece in the button battery, and soak in dimethyl carbonate (DMC) for 8 hours. Then dry, scrape the powder, and screen out the particles whose particle size is less than 500nm. The obtained particles were measured by electron energy loss spectroscopy (EELS, the instrument model used was Talos F200S), and the energy loss near-edge structure (ELNES) was obtained, which reflected the density of states and energy level distribution of the elements. According to the density of states and energy level distribution, the number of occupied electrons is calculated by integrating the data of the valence band density of states, so as to calculate the valence state of the charged surface oxygen.
  • DMC dimethyl carbonate
  • the positive electrode active material powder prepared above Take 5g of the positive electrode active material powder prepared above, and measure the total scattering intensity by X-rays, which is the sum of the scattering intensity of the entire space material, and is only related to the intensity of the primary ray, the chemical structure, and the total number of electrons participating in the diffraction, that is, the mass. It is related, but not related to the order state of the sample; then the crystalline scattering and the non-crystalline scattering are separated from the diffraction pattern, and the degree of crystallinity is the ratio of the crystalline partial scattering to the total scattering intensity.
  • the existence of the first cladding layer is beneficial to reduce the Li/Mn antisite defect concentration of the obtained material and the amount of Fe and Mn dissolved after cycling, and improve the battery performance. Reduce battery capacity and improve battery safety and cycle performance.
  • the lattice change rate, antisite defect concentration and Fe and Mn dissolution amount of the obtained material can be significantly reduced, the gram capacity of the battery can be increased, and the safety performance and cycle of the battery can be improved. performance.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

La présente demande porte sur un matériau actif d'électrode positive à structure cœur-écorce, comprenant un cœur interne et une écorce recouvrant le cœur interne, le cœur interne étant représenté par la formule Li1+xMn1-yAyP1-zRzO4, dans laquelle x = -0,100 à 0,100, y = 0,001 à 0,500, z = 0,001 à 0,100, A est choisi parmi Zn, Al, Na, K, Mg, Mo, W, Ti, V, Zr, Fe, Ni, Co, Ga, Sn, Sb, Nb et Ge, et éventuellement parmi Fe, Ti, V, Ni, Co et Mg, et R est choisi parmi B, Si, N et S ; et l'écorce comprend une première couche de revêtement recouvrant le noyau interne et une seconde couche de revêtement recouvrant la première couche de revêtement, la première couche de revêtement comprenant un pyrophosphate MP2O7 et un phosphate XPO4, M et X étant choisis indépendamment parmi au moins Li, Fe, Ni, Mg, Co, Cu, Zn, Ti, Ag, Zr, Nb ou Al, et la seconde couche de revêtement contenant du carbone.
PCT/CN2021/130350 2021-10-22 2021-11-12 Matériau actif d'électrode positive, feuille d'électrode positive, batterie secondaire, module de batterie, bloc-batterie et dispositif électrique WO2023082182A1 (fr)

Priority Applications (21)

Application Number Priority Date Filing Date Title
CN202180093423.0A CN116964774A (zh) 2021-11-12 2021-11-12 正极活性材料、正极极片、二次电池、电池模块、电池包和用电装置
PCT/CN2021/130350 WO2023082182A1 (fr) 2021-11-12 2021-11-12 Matériau actif d'électrode positive, feuille d'électrode positive, batterie secondaire, module de batterie, bloc-batterie et dispositif électrique
KR1020247008222A KR20240048003A (ko) 2021-10-22 2022-10-21 양극 활물질, 양극 극판, 이차 전지, 전지 모듈, 전지 팩 및 전기 장치
KR1020247007998A KR20240046889A (ko) 2021-10-22 2022-10-21 양극 활물질, 양극 극판, 이차 전지, 전지 모듈, 전지 팩 및 전기 장치
PCT/CN2022/126829 WO2023066393A1 (fr) 2021-10-22 2022-10-21 Matériau actif d'électrode positive, feuille d'électrode positive, batterie secondaire, module de batterie, bloc-batterie et dispositif électrique
CN202280007637.6A CN116547835A (zh) 2021-10-22 2022-10-21 正极活性材料及制备方法、正极极片、二次电池、电池模块、电池包及用电装置
CN202280013384.3A CN116964781A (zh) 2021-10-22 2022-10-21 正极活性材料、正极极片、二次电池、电池模块、电池包和用电装置
JP2024515815A JP2024533449A (ja) 2021-10-22 2022-10-21 正極活物質、正極板、二次電池、電池モジュール、電池パックおよび電力消費装置
PCT/CN2022/126838 WO2023066394A1 (fr) 2021-10-22 2022-10-21 Matériau actif d'électrode positive, feuille d'électrode positive, batterie secondaire, module de batterie, bloc-batterie et dispositif électrique
PCT/CN2022/126778 WO2023066386A1 (fr) 2021-10-22 2022-10-21 Matériau actif d'électrode positive et son procédé de préparation, pièce polaire d'électrode positive, batterie secondaire, module de batterie, bloc-batterie et dispositif consommateur d'énergie
JP2023543271A JP2024505446A (ja) 2021-10-22 2022-10-21 正極活物質及び製造方法、正極板、二次電池、電池モジュール、電池パック並びに電力消費装置
EP22882997.4A EP4418362A1 (fr) 2021-10-22 2022-10-21 Matériau actif d'électrode positive, feuille d'électrode positive, batterie secondaire, module de batterie, bloc-batterie et dispositif électrique
EP22882998.2A EP4418363A1 (fr) 2021-10-22 2022-10-21 Matériau actif d'électrode positive, feuille d'électrode positive, batterie secondaire, module de batterie, bloc-batterie et dispositif électrique
JP2024515538A JP2024534988A (ja) 2021-10-22 2022-10-21 正極活物質、正極板、二次電池、電池モジュール、電池パックおよび電力消費装置
KR1020237024611A KR20230122108A (ko) 2021-10-22 2022-10-21 양극 활물질 및 제조 방법, 양극 극판, 이차 전지, 전지 모듈, 전지 팩 및 전기 장치
AU2022371736A AU2022371736A1 (en) 2021-10-22 2022-10-21 Positive electrode active material and preparation method therefor, positive electrode pole piece, secondary battery, battery module, battery pack, and power-consuming device
CN202280013385.8A CN117121236A (zh) 2021-10-22 2022-10-21 正极活性材料、正极极片、二次电池、电池模块、电池包和用电装置
EP22882990.9A EP4261946A1 (fr) 2021-10-22 2022-10-21 Matériau actif d'électrode positive et son procédé de préparation, pièce polaire d'électrode positive, batterie secondaire, module de batterie, bloc-batterie et dispositif consommateur d'énergie
US18/351,925 US20230361296A1 (en) 2021-10-22 2023-07-13 Positive electrode active material and preparation method therefor, positive electrode plate, secondary battery, battery module, battery pack, and power consuming device
US18/641,410 US20240282969A1 (en) 2021-10-22 2024-04-21 Positive electrode active material, positive electrode plate, secondary battery, battery module, battery pack and power consuming device
US18/641,427 US20240282963A1 (en) 2021-10-22 2024-04-21 Positive electrode active material, positive electrode plate, secondary battery, battery module, battery pack and power consuming device

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/CN2021/130350 WO2023082182A1 (fr) 2021-11-12 2021-11-12 Matériau actif d'électrode positive, feuille d'électrode positive, batterie secondaire, module de batterie, bloc-batterie et dispositif électrique

Publications (1)

Publication Number Publication Date
WO2023082182A1 true WO2023082182A1 (fr) 2023-05-19

Family

ID=86334813

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2021/130350 WO2023082182A1 (fr) 2021-10-22 2021-11-12 Matériau actif d'électrode positive, feuille d'électrode positive, batterie secondaire, module de batterie, bloc-batterie et dispositif électrique

Country Status (2)

Country Link
CN (1) CN116964774A (fr)
WO (1) WO2023082182A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116914129A (zh) * 2023-09-15 2023-10-20 宁德时代新能源科技股份有限公司 正极活性材料及其制备方法、正极极片、电池和用电装置
CN117542961A (zh) * 2024-01-10 2024-02-09 宁德时代新能源科技股份有限公司 电池单体、电池及用电装置

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101339994A (zh) * 2008-09-01 2009-01-07 罗绍华 多位掺杂型磷酸铁锂正极材料制备方法及其应用
CN106058225A (zh) * 2016-08-19 2016-10-26 中航锂电（洛阳）有限公司 核壳结构LiMn1‑xFexPO4正极材料及其制备方法、锂离子电池
US20170365859A1 (en) * 2016-06-17 2017-12-21 Samsung Electronics Co., Ltd. Composite cathode active material for lithium battery, cathode for lithium battery including the same, and lithium battery including the cathode
CN109888201A (zh) * 2019-01-03 2019-06-14 北京泰丰先行新能源科技有限公司 正极活性材料、含有该正极活性材料的正极和锂二次电池
CN110416525A (zh) * 2019-08-08 2019-11-05 上海华谊（集团）公司 具有核壳结构的含磷酸锰铁锂的复合材料及其制备方法
CN112635722A (zh) * 2019-10-09 2021-04-09 北京卫蓝新能源科技有限公司 一种锂离子电池复合正极材料及制备方法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101339994A (zh) * 2008-09-01 2009-01-07 罗绍华 多位掺杂型磷酸铁锂正极材料制备方法及其应用
US20170365859A1 (en) * 2016-06-17 2017-12-21 Samsung Electronics Co., Ltd. Composite cathode active material for lithium battery, cathode for lithium battery including the same, and lithium battery including the cathode
CN106058225A (zh) * 2016-08-19 2016-10-26 中航锂电（洛阳）有限公司 核壳结构LiMn1‑xFexPO4正极材料及其制备方法、锂离子电池
CN109888201A (zh) * 2019-01-03 2019-06-14 北京泰丰先行新能源科技有限公司 正极活性材料、含有该正极活性材料的正极和锂二次电池
CN110416525A (zh) * 2019-08-08 2019-11-05 上海华谊（集团）公司 具有核壳结构的含磷酸锰铁锂的复合材料及其制备方法
CN112635722A (zh) * 2019-10-09 2021-04-09 北京卫蓝新能源科技有限公司 一种锂离子电池复合正极材料及制备方法

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116914129A (zh) * 2023-09-15 2023-10-20 宁德时代新能源科技股份有限公司 正极活性材料及其制备方法、正极极片、电池和用电装置
CN116914129B (zh) * 2023-09-15 2024-02-13 宁德时代新能源科技股份有限公司 正极活性材料及其制备方法、正极极片、电池和用电装置
CN117542961A (zh) * 2024-01-10 2024-02-09 宁德时代新能源科技股份有限公司 电池单体、电池及用电装置

Also Published As

Publication number Publication date
CN116964774A (zh) 2023-10-27

Similar Documents

Publication Publication Date Title
WO2023115388A1 (fr) Matériau actif d'électrode positive et son procédé de préparation, plaque d'électrode positive, batterie secondaire, module de batterie, bloc-batterie et dispositif électrique
WO2023066393A1 (fr) Matériau actif d'électrode positive, feuille d'électrode positive, batterie secondaire, module de batterie, bloc-batterie et dispositif électrique
WO2023164930A1 (fr) Nouvelle plaque d'électrode positive, batterie secondaire, module de batterie, bloc-batterie et dispositif électrique
WO2023082182A1 (fr) Matériau actif d'électrode positive, feuille d'électrode positive, batterie secondaire, module de batterie, bloc-batterie et dispositif électrique
WO2023206342A1 (fr) Batterie secondaire et module de batterie, bloc-batterie et dispositif électrique comprenant ceux-ci
WO2023066394A1 (fr) Matériau actif d'électrode positive, feuille d'électrode positive, batterie secondaire, module de batterie, bloc-batterie et dispositif électrique
WO2023184504A1 (fr) Matériau actif d'électrode positive et son procédé de préparation, plaque d'électrode positive le comprenant, batterie secondaire et dispositif électrique
WO2024011596A1 (fr) Matériau actif d'électrode positive, procédé de préparation de matériau actif d'électrode positive, plaque d'électrode positive, batterie secondaire, module de batterie, bloc-batterie et dispositif électrique
WO2023065359A1 (fr) Matériau actif d'électrode positive, plaque d'électrode positive, batterie secondaire, module de batterie, bloc-batterie et appareil de consommation d'énergie
WO2023206449A1 (fr) Batterie secondaire et module de batterie comprenant celle-ci, bloc-batterie et dispositif électrique
WO2023206427A1 (fr) Batterie secondaire, module de batterie la comprenant, bloc-batterie et dispositif électrique
WO2023184408A1 (fr) Matériau actif d'électrode positive et son procédé de préparation, plaque d'électrode positive le comprenant, batterie secondaire et dispositif électrique
WO2024065144A1 (fr) Matériau actif d'électrode positive, son procédé de préparation, ainsi que feuille d'électrode positive le contenant, batterie rechargeable et dispositif électrique
WO2024065145A1 (fr) Matériau actif d'électrode positive, son procédé de préparation, ainsi que feuille d'électrode positive, batterie rechargeable et dispositif électrique le comprenant
WO2023184503A1 (fr) Batterie secondaire, module de batterie, bloc-batterie et appareil électrique
WO2023184511A1 (fr) Matériau actif d'électrode positive, son procédé de préparation et plaque d'électrode positive le contenant, et batterie secondaire et appareil électrique
WO2023164926A1 (fr) Plaque d'électrode positive, batterie secondaire, module de batterie, bloc-batterie et dispositif électrique
WO2023184498A1 (fr) Batterie secondaire, module de batterie, bloc-batterie et appareil électrique
WO2023240603A1 (fr) Matériau actif d'électrode positive et son procédé de préparation, plaque d'électrode positive, batterie rechargeable, module de batterie, bloc-batterie et dispositif électrique
WO2023184489A1 (fr) Batterie secondaire, module de batterie, bloc-batterie et appareil électrique
WO2023225836A1 (fr) Matériau actif d'électrode positive, feuille d'électrode positive, batterie secondaire, module de batterie, bloc-batterie et appareil électrique
WO2024065213A1 (fr) Matériau actif d'électrode positive, son procédé de préparation, ainsi que feuille d'électrode positive, batterie rechargeable et dispositif électrique le comprenant
WO2024212189A1 (fr) Feuille d'électrode positive, batterie, et dispositif électrique
WO2023184496A1 (fr) Batterie secondaire, module de batterie, bloc-batterie, et dispositif électrique
WO2023184494A1 (fr) Matériau actif d'électrode positive et son procédé de préparation, plaque d'électrode positive le comprenant, batterie secondaire et dispositif électrique

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 21963631

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 202180093423.0

Country of ref document: CN

NENP Non-entry into the national phase

Ref country code: DE