WO2025199882A1 - Procédé de croissance in situ de lithium-fer-phosphate sur du graphène tridimensionnel et utilisation de lithium-fer-phosphate - Google Patents

Procédé de croissance in situ de lithium-fer-phosphate sur du graphène tridimensionnel et utilisation de lithium-fer-phosphate

Info

Publication number
WO2025199882A1
WO2025199882A1 PCT/CN2024/084529 CN2024084529W WO2025199882A1 WO 2025199882 A1 WO2025199882 A1 WO 2025199882A1 CN 2024084529 W CN2024084529 W CN 2024084529W WO 2025199882 A1 WO2025199882 A1 WO 2025199882A1
Authority
WO
WIPO (PCT)
Prior art keywords
source
dimensional graphene
lithium
iron phosphate
lithium iron
Prior art date
Legal status (The legal status 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 status listed.)
Pending
Application number
PCT/CN2024/084529
Other languages
English (en)
Chinese (zh)
Inventor
唐政
武义
秦瑞杰
张俊峰
杨国庆
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shenzhen Tig Technology Co Ltd
Original Assignee
Shenzhen Tig Technology Co Ltd
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 Shenzhen Tig Technology Co Ltd filed Critical Shenzhen Tig Technology Co Ltd
Priority to PCT/CN2024/084529 priority Critical patent/WO2025199882A1/fr
Publication of WO2025199882A1 publication Critical patent/WO2025199882A1/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B25/00—Phosphorus; Compounds thereof
    • C01B25/16—Oxyacids of phosphorus; Salts thereof
    • C01B25/26—Phosphates
    • C01B25/45—Phosphates containing plural metal, or metal and ammonium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—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
    • 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
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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 invention relates to the field of energy storage material production, and in particular to a method for in-situ growth of lithium iron phosphate on three-dimensional graphene and applications thereof.
  • Lithium iron phosphate batteries (LiFePO4 ) have become one of the most promising cathode materials for lithium-ion batteries due to their low cost, long cycle life, and excellent safety.
  • the material's low electrical conductivity hinders its performance at high power and low temperatures, limiting its wider application.
  • lithium iron phosphate material it is necessary to modify the lithium iron phosphate material to increase its electrical conductivity and power density, and improve its cycle performance and low-temperature performance.
  • the present invention provides a method for in-situ growth of lithium iron phosphate using three-dimensional graphene.
  • the electrical conductivity of the lithium iron phosphate growth material is greatly improved, thereby significantly increasing its power density and significantly improving its cycle performance and low-temperature performance.
  • Another object of the present invention is to provide an application of the three-dimensional graphene in-situ growth of lithium iron phosphate.
  • a method for in-situ growth of lithium iron phosphate on three-dimensional graphene comprises the following steps:
  • the iron source in step S1 is selected from any one of ferrous oxalate, ferric phosphate, ferric oxide or iron powder, or a combination of two or more thereof;
  • the phosphorus source is selected from any one of phosphoric acid, ammonium monohydrogen phosphate or ammonium dihydrogen phosphate, or a combination of two or more thereof.
  • the total molar number of the iron source and the doping element source added once in step S1 is the same as the molar number of the phosphorus source; and the molar ratio of the lithium source to the phosphorus source is (1-1.1):1.
  • the primary particle size D90 of the solid particles obtained by the primary grinding and mixing in step S1 is 10 to 300 nm.
  • the amount of three-dimensional graphene added in step S2 is 0.5% to 8% of the mass of the first grinding mixture; preferably, the three-dimensional graphene is a three-dimensional structure with a specific surface area of 500-2500 m 2 /g and a pore size of 10 nm to 2 ⁇ m.
  • the temperature of the hydrothermal reaction in step S3 is 100-300° C.
  • the reaction pressure is 0.1-2.0 MPa
  • the reaction time is 1-36 h
  • the solid content of the hydrothermal reaction material is 10-80%.
  • the secondary added doping element source in step S4 is a carbon source, selected from any one of lactose, glucose, sucrose, polyethylene glycol, or a combination of two or more thereof.
  • the sintering temperature in step S5 is 650-950° C., and the sintering time is 6-36 hours.
  • Another aspect of the present invention is the use of in-situ grown lithium iron phosphate of three-dimensional graphene prepared by the above method in lithium batteries.
  • the present invention has the following advantages:
  • the method of the present invention in situ grows lithium iron phosphate material in the pores of three-dimensional graphene. Since the three-dimensional graphene structure has ultra-high electrical conductivity, it can serve as a carrier to greatly improve the electrical conductivity of the grown material, greatly increase its power density, and significantly improve its cycle performance and low-temperature performance. At the same time, the porosity of three-dimensional graphene gives it excellent adsorption capacity and can well load other materials, providing a basis for in situ growth. The high specific surface area of three-dimensional graphene can form a double layer reaction in the ungrown pores, thereby greatly improving the pulse performance of the material and increasing the response speed of the device.
  • a method for in-situ growth of lithium iron phosphate on three-dimensional graphene comprises the following steps:
  • the second-grinding mixture of S2 is subjected to a hydrothermal reaction, and the reaction product is ground and mixed three times;
  • the iron source is selected from any one of ferrous oxalate, ferric phosphate, iron oxide or iron powder, or a combination of two or more thereof, preferably ferric oxalate;
  • the phosphorus source is selected from any one of phosphoric acid, ammonium monohydrogen phosphate or ammonium dihydrogen phosphate, or a combination of two or more thereof, preferably ammonium dihydrogen phosphate.
  • the lithium source is one of lithium carbonate or lithium hydroxide, or a combination of two or more thereof, preferably lithium carbonate;
  • the primary added doping element source is a metal element, selected from any one of Mn, Mg, Al, Zn, Ni, Co, Ca, Cu, or preferably Al or Mn.
  • the total molar number of the iron source and the primary added doping element source is the same as the molar number of the phosphorus source; the molar ratio of the lithium source to the phosphorus source is (1-1.1):1, for example, 1; 1, 1.05:1, 1.1:1, etc., all calculated based on the molar number of the corresponding elements.
  • the above-mentioned iron source, phosphorus source, lithium source and primary doping element source are added together and then wet ball milled.
  • the ball milling speed for example, 200-2000 rpm, preferably 500-1000 rpm
  • the ball milling time for example, 2-6 h.
  • the solid particles obtained by the primary grinding and mixing have a primary particle size D90 of 10 to 300 nm, for example, 30 nm, 50 nm, 75 nm, 100 nm, 150 nm, 200 nm, 250 nm, etc.
  • step S2 after the initial grinding and mixing, the raw materials are thoroughly mixed. Three-dimensional graphene is then added thereto in an amount ranging from 0.5% to 8% of the mass of the first grinding mixture, for example, including but not limited to 0.5%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, and 8%. Ball milling is then performed again to thoroughly mix the graphene and the raw materials.
  • the speed of the second ball milling is also not particularly limited, for example, 200-2000 rpm, preferably 500-1000 rpm.
  • the ball milling time is also not particularly limited, for example, 0.5-4 hours, primarily to thoroughly mix and contact the graphene with the raw materials for the next hydrothermal reaction.
  • the three-dimensional graphene is a three-dimensional structure with a specific surface area of 500-2500 m2 /g and a pore size of 10 nm-2 ⁇ m. Its porous properties provide good adsorption and a location for in-situ growth of the hydrothermal reaction.
  • the hydrothermal reaction can be carried out in a hydrothermal reactor, for example, the temperature of the hydrothermal reaction is 100-300°C, for example, 100°C, 150°C, 200°C, 250°C, 300°C, etc., the reaction pressure is 0.1-2.0 MPa, for example, 0.1 MPa, 0.5 MPa, 1.0 MPa, 1.5 MPa, 2.0 MPa, etc., the reaction time is 1-36h, for example, 2h, 5h, 8h, 10h, 15h, 20h, 25h, 30h, 35h, etc., and the solid content in the hydrothermal reaction material is 10-80%, for example, 15%, 20%, 30%, 40%, 50%, 60%, 70%, etc.
  • a doping element source is added a second time to the tertiary-milled mixture to obtain a mixed slurry.
  • the secondary doping element source is a carbon source, such as one or a combination of two or more selected from lactose, glucose, sucrose, and polyethylene glycol, preferably glucose.
  • the carbon source is added in an amount of 1-5% of the mass of the tertiary-milled mixture to obtain a mixed slurry having a solids content of 20-50%.
  • the three-dimensional graphene in-situ grown lithium iron phosphate prepared by the above method can be used as a positive electrode material and applied in lithium batteries.
  • the three-dimensional graphene in situ growth of lithium iron phosphate is prepared by the following steps:
  • the three-dimensional graphene in situ growth of lithium iron phosphate is prepared by the following steps:
  • the second grinding mixture of S2 was subjected to hydrothermal reaction at 300°C and 1.8 MPa for 30 h, and the reaction product was ground and mixed three times, and ground at a ball mill speed of 1000 rpm for about 3.5 h until the primary particle size D90 of the solid particles was 200 nm;
  • the mixed slurry obtained in S4 is spray-granulated to obtain 3 ⁇ m particles, which are sintered under a nitrogen gas protection atmosphere at a sintering temperature of 700° C. and a sintering time of 30 h.
  • the sintered material is crushed and passed through a 200-mesh sieve to obtain the three-dimensional graphene in-situ grown lithium iron phosphate.
  • the three-dimensional graphene in situ growth of lithium iron phosphate is prepared by the following steps:
  • the second grinding mixture of S2 was subjected to hydrothermal reaction at 200°C and 1.0 MPa for 15 h, and the reaction product was ground and mixed three times, and ground at a ball mill speed of 2000 rpm for about 4 h until the primary particle size D90 of the solid particles was 100 nm;
  • the positive electrode uses conductive carbon black as the conductive agent, PVDF as the binder, and NMP as the solvent.
  • the slurry is prepared according to the mass ratio of lithium iron phosphate: conductive agent: binder for the in-situ growth of three-dimensional graphene at a ratio of 94:3:3.
  • the slurry has a solid content of 48% and is coated on a 12um aluminum foil. It is then dried, rolled, and cut into pieces to make the positive electrode.
  • the negative electrode uses hard carbon as the active material, conductive carbon black as the conductive agent, SBR emulsion binder 1, CMC as binder 2, and pure water as the solvent.
  • the slurry is prepared in a mass ratio of artificial graphite, conductive agent, binder 1, and binder 2 of 95.5:2:2:1.5, with a solid content of 50%.
  • the slurry is coated on 8um copper foil, dried, rolled, and slit to form a negative electrode.
  • the positive and negative electrodes of the above three embodiments are respectively used through die-cutting, lamination, packaging, and liquid injection processes to prepare soft-pack battery cells.
  • the soft-pack battery cell has a capacity retention rate of 89.2% after 8000 cycles at a charge and discharge current of 5C and 100% SOC, showing good cycle performance.
  • the temperature performance of the soft-pack battery is as follows (5C rate discharge):
  • Example 1 Compared with Example 1, only the three-dimensional graphene is not added, and other conditions are exactly the same.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

Sont divulgués dans la présente invention un procédé de croissance in situ de lithium-fer-phosphate sur du graphène tridimensionnel et une utilisation du lithium-fer-phosphate. Le procédé consiste à : dissoudre une source de fer et une source de phosphore dans de l'eau, mélanger pour obtenir une solution de réaction, ajouter une source de lithium, ajouter un premier élément dopant et effectuer une première opération de broyage et de mélange ; ajouter du graphène tridimensionnel et effectuer une deuxième opération de broyage et de mélange ; et effectuer une réaction hydrothermique et une troisième opération de broyage et de mélange ; ajouter la seconde source d'élément dopant afin d'obtenir une suspension mélangée, effectuer une granulation par pulvérisation, fritter des particules dans une atmosphère de gaz inerte et concasser et tamiser un produit fritté pour obtenir le lithium-fer-phosphate développé in situ dur le graphène tridimensionnel. Selon le procédé de la présente invention, la croissance in situ d'un matériau lithium-fer-phosphate à l'intérieur de pores de graphène tridimensionnel améliore considérablement la conductivité électrique du matériau de croissance, ce qui permet d'augmenter considérablement la densité de puissance du matériau de croissance et d'améliorer significativement les performances de cycle et les performances à basse température du matériau de croissance.
PCT/CN2024/084529 2024-03-28 2024-03-28 Procédé de croissance in situ de lithium-fer-phosphate sur du graphène tridimensionnel et utilisation de lithium-fer-phosphate Pending WO2025199882A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PCT/CN2024/084529 WO2025199882A1 (fr) 2024-03-28 2024-03-28 Procédé de croissance in situ de lithium-fer-phosphate sur du graphène tridimensionnel et utilisation de lithium-fer-phosphate

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/CN2024/084529 WO2025199882A1 (fr) 2024-03-28 2024-03-28 Procédé de croissance in situ de lithium-fer-phosphate sur du graphène tridimensionnel et utilisation de lithium-fer-phosphate

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Publication Number Publication Date
WO2025199882A1 true WO2025199882A1 (fr) 2025-10-02

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101752561A (zh) * 2009-12-11 2010-06-23 中国科学院宁波材料技术与工程研究所 石墨烯改性磷酸铁锂正极活性材料及其制备方法以及锂离子二次电池
CN102185139A (zh) * 2011-03-31 2011-09-14 中国科学院过程工程研究所 一种纳米金属氧化物/石墨烯掺杂磷酸铁锂电极材料的制备方法
US20120032119A1 (en) * 2009-03-13 2012-02-09 Jfe Chemical Corporation Method for producing lithium iron phosphate
CN110921643A (zh) * 2019-12-06 2020-03-27 联动天翼新能源有限公司 一种磷酸铁锂的水热制备方法及高压实磷酸铁锂
CN111217347A (zh) * 2018-11-23 2020-06-02 深圳市贝特瑞纳米科技有限公司 一种高压实磷酸铁锂材料及其制备方法
CN116093312A (zh) * 2022-12-14 2023-05-09 深圳市今朝时代股份有限公司 一种三维石墨烯原位生长磷酸铁锂的方法及其应用

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20120032119A1 (en) * 2009-03-13 2012-02-09 Jfe Chemical Corporation Method for producing lithium iron phosphate
CN101752561A (zh) * 2009-12-11 2010-06-23 中国科学院宁波材料技术与工程研究所 石墨烯改性磷酸铁锂正极活性材料及其制备方法以及锂离子二次电池
CN102185139A (zh) * 2011-03-31 2011-09-14 中国科学院过程工程研究所 一种纳米金属氧化物/石墨烯掺杂磷酸铁锂电极材料的制备方法
CN111217347A (zh) * 2018-11-23 2020-06-02 深圳市贝特瑞纳米科技有限公司 一种高压实磷酸铁锂材料及其制备方法
CN110921643A (zh) * 2019-12-06 2020-03-27 联动天翼新能源有限公司 一种磷酸铁锂的水热制备方法及高压实磷酸铁锂
CN116093312A (zh) * 2022-12-14 2023-05-09 深圳市今朝时代股份有限公司 一种三维石墨烯原位生长磷酸铁锂的方法及其应用

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