WO2023065359A1 - Matériau actif d'électrode positive, plaque d'électrode positive, batterie secondaire, module de batterie, bloc-batterie et appareil de consommation d'énergie - Google Patents

Matériau actif d'électrode positive, plaque d'électrode positive, batterie secondaire, module de batterie, bloc-batterie et appareil de consommation d'énergie Download PDF

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Publication number
WO2023065359A1
WO2023065359A1 PCT/CN2021/125898 CN2021125898W WO2023065359A1 WO 2023065359 A1 WO2023065359 A1 WO 2023065359A1 CN 2021125898 W CN2021125898 W CN 2021125898W WO 2023065359 A1 WO2023065359 A1 WO 2023065359A1
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WO
WIPO (PCT)
Prior art keywords
positive electrode
active material
electrode active
range
source
Prior art date
Application number
PCT/CN2021/125898
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English (en)
Chinese (zh)
Inventor
蒋耀
欧阳楚英
张欣欣
邓斌
王志强
袁天赐
徐波
陈尚栋
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宁德时代新能源科技股份有限公司
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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 CN202180090081.7A priority Critical patent/CN116802846A/zh
Priority to PCT/CN2021/125898 priority patent/WO2023065359A1/fr
Priority to PCT/CN2022/126778 priority patent/WO2023066386A1/fr
Priority to EP22882997.4A priority patent/EP4418362A1/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/CN2022/126829 priority patent/WO2023066393A1/fr
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 WO2023065359A1 publication Critical patent/WO2023065359A1/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

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • 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 lattice change rate of the positive electrode active material is less than 8%, optionally less than 4%.
  • the rate performance of the battery cell can be improved.
  • the first aspect of the present application proposes a positive electrode active material having the chemical formula Li a A x Mn 1-y By y P 1-z C z O 4-n D n ,
  • the lattice change rate during the delithiation process can be further reduced, thereby further improving the rate performance of the battery.
  • the Mn-site doping elements within the above range the electronic conductivity can be further improved and the lattice change rate can be further reduced, thereby improving the rate performance and gram capacity of the battery.
  • the P-site doping element within the above range the rate performance of the battery can be further improved.
  • the side reactions at the interface can be further reduced, and the high-temperature performance of the battery can be improved.
  • the lattice change rate of the positive electrode active material is less than 8%, optionally, the lattice change rate is less than 4%.
  • the lattice change rate By reducing the lattice change rate, Li ion transport can be made easier, that is, Li ion has a stronger mobility in the material, which is beneficial to improve the rate performance of the secondary battery.
  • the rate of lattice change can be measured by methods known in the art, such as X-ray diffraction (XRD).
  • step (3) Sintering the particles obtained in step (3) to obtain a positive electrode active material.
  • the phosphorus source can be a phosphorus-containing substance known in the art that can be used to prepare lithium manganese phosphate, for example, the phosphorus source can be selected from diammonium hydrogen phosphate, ammonium dihydrogen phosphate, ammonium phosphate and phosphoric acid one or a combination of them.
  • the stirring in step (1) is performed at a temperature in the range of 60-120°C. In some embodiments, the stirring in step (1) is performed at a stirring rate of 200-800 rpm, or 300-800 rpm, or 400-800 rpm. In some embodiments, the agitation of step (1) is performed for 6-12 hours. In some embodiments, the milling and mixing of step (2) is performed for 8-15 hours.
  • the filter cake may be washed before drying the filter cake in step (1).
  • 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 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 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 secondary battery may include an outer package.
  • the outer package can be used to package the above-mentioned electrode assembly and electrolyte.
  • the secondary battery can be assembled into a battery module, and the number of secondary 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.
  • 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 above-mentioned positive electrode active material, polyvinylidene fluoride (PVDF), and acetylene black were added to N-methylpyrrolidone (NMP) in a weight ratio of 90:5:5, and stirred in a drying room to form a slurry.
  • NMP N-methylpyrrolidone
  • 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 .
  • Full cells were stored at 100% state of charge (SOC) at 60°C.
  • 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 battery of the embodiment always maintains an SOC of more than 99% during the experiment until the end of storage.
  • Table 1 shows the positive electrode active material compositions of Examples 1-11 and Comparative Examples 1-8.
  • Table 2 shows the performance data of the positive electrode active materials of Examples 1-11 and Comparative Examples 1-8, either button-charged or full-charged, measured according to the above-mentioned performance test method.
  • Table 3 shows the positive electrode active material compositions of Examples 12-27.
  • Table 4 shows the performance data of the positive electrode active materials of Examples 12-27 measured according to the above-mentioned performance test method, either button-charged or full-charged.
  • the performance data of the positive electrode active material of the embodiment 28-41 of table 6 or buckle electricity or full electricity is measured according to the above-mentioned performance test method
  • Example 42 LiOH MnCO 3 NH 4 H 2 PO 4 Mo(NO 3 ) 6 FeO H 4 SiO 4 NH 4 F
  • Example 43 LiOH MnO NH 4 H 2 PO 4 Mo(NO 3 ) 6 FeO H 4 SiO 4 NH 4 F
  • Example 44 LiOH Mn 3 O 4 NH 4 H 2 PO 4 Mo(NO 3 ) 6 FeO H 4 SiO 4 NH 4 F
  • Example 46 LiOH MnO NH 4 H 2 PO 4 Mo(NO 3 ) 6 FeCO 3 H 4 SiO 4 NH 4 F
  • Example 47 LiOH MnO NH 4 H 2 PO 4 Mo(NO 3 ) 6 Fe(NO 3 ) 2 H 4 SiO 4 NH 4 F
  • Example 48 LiOH MnO NH 4 H 2 PO 4 Mo
  • the performance data of the positive electrode active material of the embodiment 42-54 of table 8 or buckle electricity or full electricity is measured according to the above-mentioned performance test method
  • (1-y):y is in the range of 1 to 4, which can further improve the energy density of the secondary battery and cycle performance.
  • FIG. 1 shows the XRD patterns of undoped LiMnPO 4 and the cathode active material prepared in Example 2. It can be seen from the figure that the position of the main characteristic peaks in the XRD diagram of the positive electrode active material of Example 2 is consistent with that of undoped LiMnPO 4 , indicating that the doping process does not introduce impurity phases, and the improvement in performance is mainly due to element doping , not caused by impurity.
  • FIG. 2 shows the EDS spectrum of the positive electrode active material prepared in Example 2. Dotted distribution in the figure is each doping element. It can be seen from the figure that in the positive electrode active material of Example 2, elements are uniformly doped.

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

Abstract

La présente demande concerne un matériau actif d'électrode positive ayant une formule chimique de LiaAxMn1-yByP1-zCzO4-nDn, A comprenant un ou plusieurs éléments choisis parmi Zn, Al, Na, K, Mg, Nb, Mo et W, B comprenant un ou plusieurs éléments choisis parmi Ti, V, Zr, Fe, Ni, Mg, Co, Ga, Sn, Sb, Nb et Ge, C comprenant un ou plusieurs éléments choisis parmi B, S, Si et N, D comprenant un ou plusieurs éléments choisis parmi S, F, Cl et Br, a étant choisi dans la plage comprise entre 0,9 et 1,1, x étant choisi dans la plage comprise entre 0,001 et 0,1, y étant choisi dans la plage comprise entre 0,001 et 0,5, z étant choisi dans la plage comprise entre 0,001 et 0,1, n étant choisi dans la plage comprise entre 0,001 et 0,1, et le matériau actif positif étant électriquement neutre. Le matériau actif d'électrode positive a une capacité de débit améliorée ; et lorsque le matériau actif d'électrode positive est utilisé pour une batterie secondaire, la dissolution de Mn et d'éléments dopants de position Mn est significativement réduite, et une performance de cycle significativement améliorée et une stabilité à haute température sont obtenues.
PCT/CN2021/125898 2021-10-22 2021-10-22 Matériau actif d'électrode positive, plaque d'électrode positive, batterie secondaire, module de batterie, bloc-batterie et appareil de consommation d'énergie WO2023065359A1 (fr)

Priority Applications (21)

Application Number Priority Date Filing Date Title
CN202180090081.7A CN116802846A (zh) 2021-10-22 2021-10-22 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/CN2021/125898 WO2023065359A1 (fr) 2021-10-22 2021-10-22 Matériau actif d'électrode positive, plaque d'électrode positive, batterie secondaire, module de batterie, bloc-batterie et appareil de consommation d'énergie
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
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/CN2022/126829 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
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)

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PCT/CN2021/125898 WO2023065359A1 (fr) 2021-10-22 2021-10-22 Matériau actif d'électrode positive, plaque d'électrode positive, batterie secondaire, module de batterie, bloc-batterie et appareil de consommation d'énergie

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Cited By (1)

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CN107706402A (zh) * 2017-11-16 2018-02-16 东北大学秦皇岛分校 一种金属元素共掺杂的磷酸锰锂/碳复合正极材料及其制备方法

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CN102456881A (zh) * 2010-10-18 2012-05-16 中国科学院物理研究所 橄榄石型磷酸盐正极材料、其制备方法及含该正极材料的正极和电池
CN103682266A (zh) * 2013-09-27 2014-03-26 广州有色金属研究院 一种Li、Mn位共掺杂磷酸锰锂/碳复合材料及其制备方法
US20150372302A1 (en) * 2014-06-18 2015-12-24 Wildcat Discovery Technologies, Inc. High energy cathode materials and methods of making and use
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Publication number Priority date Publication date Assignee Title
CN116525817A (zh) * 2023-07-04 2023-08-01 宁波容百新能源科技股份有限公司 正极活性材料及其制备方法、正极片和二次电池
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