WO2020168974A1 - Lithium iron phosphate battery and preparation method therefor - Google Patents

Lithium iron phosphate battery and preparation method therefor Download PDF

Info

Publication number
WO2020168974A1
WO2020168974A1 PCT/CN2020/075052 CN2020075052W WO2020168974A1 WO 2020168974 A1 WO2020168974 A1 WO 2020168974A1 CN 2020075052 W CN2020075052 W CN 2020075052W WO 2020168974 A1 WO2020168974 A1 WO 2020168974A1
Authority
WO
WIPO (PCT)
Prior art keywords
iron phosphate
lithium iron
parts
phosphate battery
negative electrode
Prior art date
Application number
PCT/CN2020/075052
Other languages
French (fr)
Chinese (zh)
Inventor
平松雄二
那须野豪三
Original Assignee
叶小剑
平松雄二
牛尾顺一
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 叶小剑, 平松雄二, 牛尾顺一 filed Critical 叶小剑
Priority to JP2021547314A priority Critical patent/JP2022527237A/en
Priority to KR1020217030181A priority patent/KR20210148121A/en
Publication of WO2020168974A1 publication Critical patent/WO2020168974A1/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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/152—Fullerenes
    • C01B32/154—Preparation
    • 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
    • H01M10/04—Construction or manufacture in general
    • 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
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0567—Liquid materials characterised by the additives
    • 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
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0569—Liquid materials characterised by the solvents
    • 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
    • H01M10/058—Construction or manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1397—Processes of manufacture of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • 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
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • H01M4/623—Binders being polymers fluorinated polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0025—Organic electrolyte
    • H01M2300/0028—Organic electrolyte characterised by the solvent
    • H01M2300/0037—Mixture of solvents
    • H01M2300/004—Three solvents

Definitions

  • the invention relates to the field of batteries, in particular to a lithium iron phosphate battery and a preparation method thereof.
  • Lithium-ion secondary batteries are widely used in electric vehicles and consumer electronic products due to their advantages of high energy density, high output power, long cycle life and low environmental pollution.
  • Lithium iron phosphate is currently one of the most commonly used cathode materials for power batteries due to its high cycle life, good safety and low price.
  • the disadvantage of lithium iron phosphate batteries is their low energy density. In order to increase the energy density, on the one hand, it is to increase the gram capacity of the positive and negative materials, and on the other hand, it is to increase the compaction density of the positive and negative electrodes.
  • the purpose of the present invention is to provide a lithium iron phosphate battery, which can solve the problem of poor wettability of the high-density electrode sheet and the electrolyte, and improve the low-temperature performance, normal temperature and high temperature of the lithium iron phosphate battery. Cycle performance has been improved, effectively extending the service life of lithium iron phosphate batteries.
  • a lithium iron phosphate battery the positive electrode material of which contains the following components: lithium iron phosphate, conductive agent, binder, carbon nanotube slurry or graphene; the negative electrode material contains the following Components: graphite carbon black, conductive agent, binder, fullerene, nanowire, nano titanium; and electrolyte, which includes catechol diacetate.
  • the positive electrode material contains the following components by weight: 2-10 parts of lithium iron phosphate, 5-30 parts of conductive agent, 1-15 parts of binder, 2.5-30 parts of carbon nanotube slurry or graphene
  • the negative electrode material contains the following components by weight: 1-20 parts of graphite carbon black, 5-30 parts of conductive agent, 1-15 parts of binder, 0.8-25 parts of fullerene, 5-15 parts of nanowire Parts, 2-8 parts of nano titanium, the mass fraction of catechol diacetate is 5-12%.
  • the positive electrode is aluminum foil.
  • the negative electrode set is copper foil.
  • the conductive agent is acetylene black.
  • the binder is polyvinylidene fluoride (PVDF).
  • the present invention also provides a method for preparing the lithium iron phosphate battery as described above, including the following steps:
  • the fullerene needs to be extracted before the step (1), and the extraction method adopts the following steps: put the carbon powder into the redox kettle and energize and burn, then extract the carbon black particles attached to the inner wall of the kettle, and then pass the electrostatic The fullerene is obtained by processing.
  • the electrolyte solution needs to be prepared before the step (1), which is prepared by the following method: mixing the organic solvent ethyl methyl carbonate, dimethyl carbonate, and methyl propionate, and finally adding catechol diacetate The added amount is 2-10% of the total volume of the electrolyte to obtain the electrolyte.
  • the step (2) negative electrode material is prepared by the following method: graphite carbon black, conductive agent, binder, fullerene, nanowire, and nano titanium are mixed and ground into powder, and the powder is moved to a pressure In a 30-50mPa high-pressure reactor, the reactor is then placed in a microwave oven with a power of 1800-2200W, heated for 200-1200s, and cooled to room temperature to obtain the negative electrode material.
  • the present invention adds nanowires and nanometer titanium to the negative electrode material of the battery; adds catechol diacetate to the electrolyte, so that the lithium iron phosphate battery of the present invention can solve high pressure
  • the poor wettability of the density electrode sheet and the electrolyte improves the low temperature performance, normal temperature and high temperature cycle performance of the lithium iron phosphate battery, and effectively extends the service life of the lithium iron phosphate battery.
  • Fig. 1 is a picture of an electrostatic loader used in preparing fullerenes in an embodiment of the present invention.
  • the graphite carbon black described in the present invention is graphitized carbon black.
  • the electrolyte of the embodiment of the present invention is composed of a lithium salt and an organic solvent.
  • the electrolyte of the present invention adopts an improved organic solvent, which can effectively provide battery performance.
  • the addition of fullerene to the negative electrode slurry can greatly improve the overall performance of the product.
  • the addition amount of fullerene can be more than four ten thousandths, and a small amount of fullerene is added.
  • the fullerene added to the negative electrode slurry is a combination of 70% positively charged fullerene and 30% negatively charged fullerene.
  • the fullerene combination with positive and negative charges is put into the battery negative electrode slurry at a mass ratio of 3 to 7%.
  • the Fuqin Dilute extracted by the invention can even be directly applied to the battery without refining by the toluene method.
  • the negative material section has a significant impact on the energy density, service life and safety of the battery.
  • the use of the fullerene prepared by the present invention in the negative electrode will help increase the charge conduction speed, the insulation between the electrodes, and can suppress the volume change of the electrode due to charging and discharging, so as to produce higher capacity and longer service life , A battery with higher safety (not easy to catch fire and explode).
  • this method can be mass-produced and obtain relatively inexpensive fullerenes.
  • the positive electrode material of the lithium iron phosphate battery of this embodiment includes the following components: 2 parts of lithium iron phosphate, 5 parts of conductive agent, 1 part of binder, and 2.5 parts of carbon nanotube slurry; the negative electrode material contains the following parts by weight Components: 1 part of graphite carbon black, 5 parts of conductive agent, 1 part of binder, 0.8 parts of fullerene, 5 parts of nanowires, 2 parts of nano-titanium, mass fraction of the catechol diacetate Is 5%.
  • the smoke obtained after burning in step 1) is input into the electrostatic generator (ie, electrostatic loader, as shown in Figure 1, the model is GC50S-N, the input voltage is AC100V50/60Hz, and the maximum output voltage is DC50kV (fixed) , The maximum output current is 20 ⁇ A, the power consumption is 10VA, the effective distance is 50-250mm, and the grounding is less than 100 ⁇ .)
  • the smoke is loaded in the electrostatic loading machine according to the positive and negative polarity to obtain positively charged fullerene and belt Negatively charged fullerenes, and then these charged fullerene mixtures are refined by the toluene method, and the refined fullerenes are 70% positively charged and 30% negatively charged.
  • the fullerene raw material in the negative electrode slurry is obtained.
  • organic solvent ethyl methyl carbonate, dimethyl carbonate, and methyl propionate are mixed, and finally catechol diacetate is added in an amount of 2% of the total volume of the electrolyte to obtain the electrolyte.
  • the negative electrode material is prepared by the following method: graphite carbon black, conductive agent, binder, fullerene, nanowire, and nano titanium are mixed and ground into powder, and the powder is moved to a high-pressure reactor with a pressure of 50 mPa , And then place the reaction kettle in a microwave oven with a power of 1800W, heat it for 1200s, and cool to room temperature to obtain the negative electrode material.
  • the positive electrode material contains the following components: 10 parts of lithium iron phosphate, 30 parts of conductive agent, 15 parts of binder, and 30 parts of carbon nanotube slurry;
  • the negative electrode material contains the following parts by weight Components: 20 parts of graphite carbon black, 30 parts of conductive agent, 15 parts of binder, 25 parts of fullerene, 15 parts of nanowires, 8 parts of nano-titanium, mass fraction of the catechol diacetate Is 12%.
  • the preparation method of the lithium iron phosphate battery in this embodiment adopts the same preparation method as in Example 1.
  • the method for extracting fullerenes in this embodiment adopts the same extraction method as in Example 1.
  • organic solvent ethyl methyl carbonate, dimethyl carbonate, and methyl propionate are mixed, and finally catechol diacetate is added in an amount of 10% of the total volume of the electrolyte to obtain the electrolyte.
  • the negative electrode material is prepared by the following method: graphite carbon black, conductive agent, binder, fullerene, nanowire, and nano titanium are mixed and ground into powder, and the powder is moved to a high pressure reactor with a pressure of 30 mPa , And then place the reaction kettle in a microwave oven with a power of 2200W, heat it for 200s, and cool to room temperature to obtain the negative electrode material.
  • the positive electrode material includes the following components: 7 parts of lithium iron phosphate, 15 parts of conductive agent, 7 parts of binder, and 15 parts of carbon nanotube slurry;
  • the negative electrode material contains the following parts by weight Components: 10 parts of graphite carbon black, 15 parts of conductive agent, 8 parts of binder, 12 parts of fullerene, 10 parts of nanowires, 5 parts of nano-titanium, mass fraction of the catechol diacetate Is 10%.
  • the preparation method of the lithium iron phosphate battery in this embodiment adopts the same preparation method as in Example 1.
  • the extraction method of fullerene in this embodiment adopts the same extraction method as that in embodiment 1.
  • the preparation method of the negative electrode material in this embodiment adopts the same preparation method as in Example 1.
  • the organic solvent ethyl methyl carbonate, dimethyl carbonate, and methyl propionate are mixed, and finally catechol diacetate is added, and the addition amount is 5% of the total volume of the electrolyte to obtain the electrolyte.
  • the positive electrode material includes the following components: 7 parts of lithium iron phosphate, 22 parts of conductive agent, 13 parts of binder, and 10 parts of graphene;
  • the negative electrode material includes the following components by weight: Graphite carbon black 12 parts, conductive agent 25 parts, binder 11 parts, fullerene 0.03 parts, nanowires 8 parts, nano titanium 3 parts.
  • the electrostatic loading machine means an Electrostatic Generator.
  • the electrostatic generator can process combustible items (such as logs into charcoal, logs are combustible items, including ore, cobblestone, etc.) ) Generate static electricity.
  • catechol diacetate and lithium salt The addition amount of catechol diacetate is the total volume of the electrolyte 2%, the electrolyte is obtained.
  • the negative electrode material is prepared by the following method: graphite carbon black, conductive agent, binder, fullerene, nanowire, and nano titanium are mixed and ground into powder, and the powder is moved to a high pressure reactor with a pressure of 40 mPa Then, the reaction kettle was placed in a microwave oven with a power of 1900w, heated for 1000s, and cooled to room temperature to obtain the negative electrode material.
  • the positive electrode material contains the following components: 6 parts of lithium iron phosphate, 15 parts of conductive agent, 8 parts of binder, and 10 parts of carbon nanotube slurry;
  • the negative electrode material contains the following parts by weight Components: 17 parts of graphite carbon black, 9 parts of conductive agent, 11 parts of binder, 2.5 parts of fullerene, 8 parts of nanowire, 3 parts of nano titanium.
  • catechol diacetate and lithium salt The addition amount of catechol diacetate is the total volume of the electrolyte 10%, the electrolyte is obtained.
  • the negative electrode material is prepared by the following method: graphite carbon black, conductive agent, binder, fullerene, nanowire, and nano titanium are mixed and ground into powder, and the powder is moved to a high-pressure reactor with a pressure of 45 mPa Then, the reaction kettle was placed in a microwave oven with a power of 2000w, heated for 700s, and cooled to room temperature to obtain the negative electrode material.
  • Comparative Example 2 The only difference between Comparative Example 2 and Example 1 is that the negative electrode material does not contain fullerenes, nanowires, and nanometer titanium.
  • Comparative Example 3 The difference between Comparative Example 3 and Example 1 is that fullerene is not included in the negative electrode material.
  • the lithium iron phosphate batteries prepared in the foregoing Examples 1-5 and Comparative Examples 1-3 were tested, and the test indicators and test results are as follows.
  • the ratio of discharge capacity to charge capacity is the discharge capacity retention rate.
  • Lithium iron phosphate battery discharge capacity retention rate (%) at -10°C CDT/CC ⁇ 100%.
  • the lithium iron phosphate battery was first discharged to 2.0V at 1C and then subjected to a cycle test. Charge to 3.6V with a constant current of 1C, then charge with a constant voltage to a current of 0.05C, and then discharge to 2.0V with a constant current of 1C. Then charge/discharge, calculate the capacity retention rate of the lithium iron phosphate battery at 25°C for 1000 cycles.
  • the capacity retention rate (%) of the lithium iron phosphate battery after 1000 cycles at 25°C the discharge capacity at the 1000th cycle/the discharge capacity at the first cycle ⁇ 100%.
  • the lithium iron phosphate battery was first discharged to 2.0V at 1C and then subjected to a cycle test.
  • the oven is heated to 60°C, charged with 1C constant current to 3.6V, then charged with constant voltage to a current of 0.05C, and then discharged with 1C constant current to 2.0V, so charge/discharge, calculate the lithium iron phosphate battery to cycle 500 at 60°C Capacity retention rate.
  • the capacity retention rate of the lithium iron phosphate battery after 500 cycles at 60°C (%) discharge capacity at the 500th cycle/discharge capacity at the first cycle ⁇ 100%.
  • Comparative Example 1 It can be seen from Comparative Example 1 that the compaction density of the positive and negative electrode membranes is increased, and the performance of the lithium iron phosphate battery drops rapidly without adding catechol diacetate. From Comparative Example 2, it can be seen that Since fullerenes, nanowires, and nano-titanium are not added to the negative electrode material, the compaction density of the negative electrode membrane of the lithium iron phosphate battery of Comparative Examples 2-3 is much lower than the embodiment of the present invention.
  • Vibration test Put it in a vibration tester and vibrate back and forth for 30 minutes, the appearance and performance remain unchanged;
  • Screwdriver penetration test After the screwdriver penetrates the battery, the voltage does not change (generally the battery will be short-circuited and the voltage is zero due to penetration), and there will be a 6-7° heating up after 6-7 minutes;

Abstract

Disclosed is a lithium iron phosphate battery. A positive electrode material thereof comprises the following components: lithium iron phosphate, a conductive agent, an adhesive, a carbon nanotube paste, or grapheme; a negative electrode material comprises the following components: a graphitized carbon black, a conductive agent, an adhesive, fullerene, a nanowire, and nano titanium; and an electrolyte, the electrolyte comprises pyrocatechol diacetate. In the present invention, the nanowire and nano titanium are added into the negative electrode material of the battery, and pyrocatechol diacetate is added into the electrolyte, so that the lithium iron phosphate battery of the present invention can solve the problem that the wettability of a high-compact density electrode sheet and the electrolyte is poor, the low-temperature performance, room-temperature and high-temperature cycling performance of the lithium iron phosphate battery can be improved, and the service life of the lithium iron phosphate battery is effectively prolonged.

Description

一种磷酸铁锂电池及其制备方法Lithium iron phosphate battery and preparation method thereof 技术领域Technical field
本发明涉及电池领域，尤其涉及一种磷酸铁锂电池及其制备方法。The invention relates to the field of batteries, in particular to a lithium iron phosphate battery and a preparation method thereof.
背景技术Background technique
锂离子二次电池由于具备能量密度大、输出功率高、循环寿命长和环境污染小等优点而被广泛应用于电动汽车以及消费类电子产品中。磷酸铁锂由于循环寿命高、安全性好及价格低廉等特性，是目前动力电池最常用的正极材料之一。磷酸铁锂电池的缺点是其能量密度偏低。为提高能量密度，一方面是增加正负极材料的克容量，另一方面是增加正负极膜片的压实密度。但是压实密度提高后会导致锂离子的扩散困难，同时电极片与电解液的浸润性变差，使得磷酸铁锂电池的循环寿命减少。因此需要从电解液角度改善高压实密度电极片体系下磷酸铁锂电池的性能。Lithium-ion secondary batteries are widely used in electric vehicles and consumer electronic products due to their advantages of high energy density, high output power, long cycle life and low environmental pollution. Lithium iron phosphate is currently one of the most commonly used cathode materials for power batteries due to its high cycle life, good safety and low price. The disadvantage of lithium iron phosphate batteries is their low energy density. In order to increase the energy density, on the one hand, it is to increase the gram capacity of the positive and negative materials, and on the other hand, it is to increase the compaction density of the positive and negative electrodes. However, an increase in the compaction density will cause difficulty in the diffusion of lithium ions, and at the same time the wettability of the electrode sheet and the electrolyte will become poor, which will reduce the cycle life of the lithium iron phosphate battery. Therefore, it is necessary to improve the performance of the lithium iron phosphate battery under the high-pressure compacted electrode sheet system from the perspective of electrolyte.
发明内容Summary of the invention
鉴于背景技术中存在的问题，本发明的目的在于提供一种磷酸铁锂电池，其能够解决高压实密度电极片与电解液浸润性差的问题，使磷酸铁锂电池的低温性能、常温和高温循环性能都得到改善，有效延长磷酸铁锂电池的使用寿命。In view of the problems in the background art, the purpose of the present invention is to provide a lithium iron phosphate battery, which can solve the problem of poor wettability of the high-density electrode sheet and the electrolyte, and improve the low-temperature performance, normal temperature and high temperature of the lithium iron phosphate battery. Cycle performance has been improved, effectively extending the service life of lithium iron phosphate batteries.
本发明通过以下技术方案来实现上述目的：一种磷酸铁锂电池，其正极材料包含以下组分：磷酸铁锂、导电剂、粘合剂、碳纳米管浆料或石墨烯；负极材料包含以下组分：石墨碳黑、导电剂、粘合剂、富勒烯、纳米线、纳米钛；以及电解液，电解液包括邻苯二酚二乙酸酯。The present invention achieves the above objectives through the following technical solutions: a lithium iron phosphate battery, the positive electrode material of which contains the following components: lithium iron phosphate, conductive agent, binder, carbon nanotube slurry or graphene; the negative electrode material contains the following Components: graphite carbon black, conductive agent, binder, fullerene, nanowire, nano titanium; and electrolyte, which includes catechol diacetate.
优选地，所述正极材料包含以下重量份的组分：磷酸铁锂2‐10份、导电剂 5‐30份、粘合剂1‐15份、碳纳米管浆料或石墨烯2.5‐30份；所述负极材料包含以下重量份的组分：石墨碳黑1‐20份、导电剂5‐30份、粘合剂1‐15份、富勒烯0.8‐25份、纳米线份5‐15份、纳米钛2‐8份，所述邻苯二酚二乙酸酯的质量分数为5‐12％。Preferably, the positive electrode material contains the following components by weight: 2-10 parts of lithium iron phosphate, 5-30 parts of conductive agent, 1-15 parts of binder, 2.5-30 parts of carbon nanotube slurry or graphene The negative electrode material contains the following components by weight: 1-20 parts of graphite carbon black, 5-30 parts of conductive agent, 1-15 parts of binder, 0.8-25 parts of fullerene, 5-15 parts of nanowire Parts, 2-8 parts of nano titanium, the mass fraction of catechol diacetate is 5-12%.
优选地，所述正极为铝箔。Preferably, the positive electrode is aluminum foil.
优选地，所述负极集为铜箔。Preferably, the negative electrode set is copper foil.
优选地，所述导电剂为乙炔黑。Preferably, the conductive agent is acetylene black.
优选地，所述粘合剂为聚偏氟乙烯(PVDF)。Preferably, the binder is polyvinylidene fluoride (PVDF).
本发明还提供一种制备如上所述磷酸铁锂电池的制备方法，包括以下步骤：The present invention also provides a method for preparing the lithium iron phosphate battery as described above, including the following steps:
(1)配料：将磷酸铁锂、导电剂、粘合剂、碳纳米管浆料进行混合得到混合正极浆料；将石墨碳黑、导电剂、粘合剂、富勒烯、纳米线、纳米钛进行混合得到混合负极浆料；(1) Ingredients: mix lithium iron phosphate, conductive agent, binder, and carbon nanotube slurry to obtain mixed positive electrode slurry; combine graphite carbon black, conductive agent, binder, fullerene, nanowire, nano Titanium is mixed to obtain a mixed negative electrode slurry;
(2)涂布：将上述正极浆料通过涂布机涂于正极上；将负极浆料通过涂布机涂于负极上；(2) Coating: coating the above-mentioned positive electrode slurry on the positive electrode through a coating machine; coating the negative electrode slurry on the negative electrode through a coating machine;
(3)然后经过辊压、分切、制片、卷绕、装配、顶侧封、烘干、注入电解液、化成，最后进行包装，获得本发明的电池。(3) After rolling, slitting, sheeting, winding, assembling, top-side sealing, drying, electrolyte injection, forming, and finally packaging, the battery of the present invention is obtained.
优选地，所述步骤(1)之前还需提取富勒烯，其提取方法采用以下步骤：将碳粉放入氧化还原釜通电燃烧，然后提取附在釜内壁的碳气黑微粒，再通过静电加工即得所述富勒烯。Preferably, the fullerene needs to be extracted before the step (1), and the extraction method adopts the following steps: put the carbon powder into the redox kettle and energize and burn, then extract the carbon black particles attached to the inner wall of the kettle, and then pass the electrostatic The fullerene is obtained by processing.
优选地，所述步骤(1)之前还需制备电解液，采用以下方法制备：将有机溶剂碳酸甲乙酯、碳酸二甲酯、丙酸甲酯混合，最后加入邻苯二酚二乙酸酯，添加量为电解液总体积的2～10％，即得所述电解液。Preferably, the electrolyte solution needs to be prepared before the step (1), which is prepared by the following method: mixing the organic solvent ethyl methyl carbonate, dimethyl carbonate, and methyl propionate, and finally adding catechol diacetate The added amount is 2-10% of the total volume of the electrolyte to obtain the electrolyte.
优选地，所述步骤(2)负极材料采用以下方法制备：将石墨碳黑、导电剂、粘合剂、富勒烯、纳米线、纳米钛混合后研磨成粉，将粉体移至压力为30～50mPa高压反应釜中，然后将反应釜放置在功率为1800～2200w的微波炉中，加热200～1200s，冷却至室温，得到所述负极材料。Preferably, the step (2) negative electrode material is prepared by the following method: graphite carbon black, conductive agent, binder, fullerene, nanowire, and nano titanium are mixed and ground into powder, and the powder is moved to a pressure In a 30-50mPa high-pressure reactor, the reactor is then placed in a microwave oven with a power of 1800-2200W, heated for 200-1200s, and cooled to room temperature to obtain the negative electrode material.
本发明的有益效果：本发明在电池的负极材料中加入纳米线、纳米钛；在电解液中加入邻苯二酚二乙酸酯，使得本发明的磷酸铁锂电池本发明能够解决高压实密度电极片与电解液浸润性差的问题，使磷酸铁锂电池的低温性能、常温和高温循环性能都得到改善，有效延长磷酸铁锂电池的使用寿命。The beneficial effects of the present invention: the present invention adds nanowires and nanometer titanium to the negative electrode material of the battery; adds catechol diacetate to the electrolyte, so that the lithium iron phosphate battery of the present invention can solve high pressure The poor wettability of the density electrode sheet and the electrolyte improves the low temperature performance, normal temperature and high temperature cycle performance of the lithium iron phosphate battery, and effectively extends the service life of the lithium iron phosphate battery.
附图说明Description of the drawings
图1为本发明实施例制备富勒烯时使用的静电加载机的图片。Fig. 1 is a picture of an electrostatic loader used in preparing fullerenes in an embodiment of the present invention.
具体实施方式detailed description
下面结合实施例对本发明进行详细说明。The present invention will be described in detail below in conjunction with embodiments.
本发明中所记载的石墨碳黑，为石墨化碳黑。The graphite carbon black described in the present invention is graphitized carbon black.
本发明实施例的电解液由锂盐和有机溶剂组成，本发明电解液采用改进型有机溶剂，能够有效提供电池性能。The electrolyte of the embodiment of the present invention is composed of a lithium salt and an organic solvent. The electrolyte of the present invention adopts an improved organic solvent, which can effectively provide battery performance.
对于本发明实施例所提供的磷酸铁锂电池，负极浆料中添加富勒烯可大大提供产品的综合性能，富勒烯的添加量在万分之四以上即可，少量添加的富勒烯引起了意想不到的效果。对于以下记载的实施例，添加在负极浆料中的富勒烯由70％带正电荷的富勒烯和30％带负电荷的富勒烯组合而成。优选地，带正负电荷的富勒烯组合按3‐7％的质量比放入电池负极浆料中。本发明提取的富勤稀甚至可以不经过甲苯法精制就可直接应用在电池上。负极材科对电池的能 量密度，使用寿命及安全性有重大影响。在负极中使用本发明制备的富勒稀将有利于提高电荷的传导速度，极间的绝缘性，并能抑制电极因充放电导致的体积变化，从而可制造出更高容量，更长使用寿命，更高安全性(不易起火，爆炸)的电池。相对于目前因不能工业化量产而显得昂贵的富勒稀，本方法可大量生产并取得较低廉的富勒稀。For the lithium iron phosphate battery provided by the embodiment of the present invention, the addition of fullerene to the negative electrode slurry can greatly improve the overall performance of the product. The addition amount of fullerene can be more than four ten thousandths, and a small amount of fullerene is added. Caused unexpected effects. For the examples described below, the fullerene added to the negative electrode slurry is a combination of 70% positively charged fullerene and 30% negatively charged fullerene. Preferably, the fullerene combination with positive and negative charges is put into the battery negative electrode slurry at a mass ratio of 3 to 7%. The Fuqin Dilute extracted by the invention can even be directly applied to the battery without refining by the toluene method. The negative material section has a significant impact on the energy density, service life and safety of the battery. The use of the fullerene prepared by the present invention in the negative electrode will help increase the charge conduction speed, the insulation between the electrodes, and can suppress the volume change of the electrode due to charging and discharging, so as to produce higher capacity and longer service life , A battery with higher safety (not easy to catch fire and explode). Compared with fullerenes, which are currently expensive because they cannot be industrialized and mass-produced, this method can be mass-produced and obtain relatively inexpensive fullerenes.
实施例1Example 1
本实施例磷酸铁锂电池，其正极材料包含以下组分：磷酸铁锂2份、导电剂5份、粘合剂1份、碳纳米管浆料2.5份；所述负极材料包含以下重量份的组分：石墨碳黑1份、导电剂5份、粘合剂1份、富勒烯0.8份、纳米线份5份、纳米钛2份，所述邻苯二酚二乙酸酯的质量分数为5％。The positive electrode material of the lithium iron phosphate battery of this embodiment includes the following components: 2 parts of lithium iron phosphate, 5 parts of conductive agent, 1 part of binder, and 2.5 parts of carbon nanotube slurry; the negative electrode material contains the following parts by weight Components: 1 part of graphite carbon black, 5 parts of conductive agent, 1 part of binder, 0.8 parts of fullerene, 5 parts of nanowires, 2 parts of nano-titanium, mass fraction of the catechol diacetate Is 5%.
本实施例磷酸铁锂电池的制备方法，包括以下步骤：The preparation method of the lithium iron phosphate battery of this embodiment includes the following steps:
(1)配料：将磷酸铁锂、导电剂、粘合剂、碳纳米管浆料进行混合得到混合正极浆料；将石墨碳黑、导电剂、粘合剂、富勒烯、纳米线、纳米钛进行混合得到混合负极浆料；(1) Ingredients: mix lithium iron phosphate, conductive agent, binder, and carbon nanotube slurry to obtain mixed positive electrode slurry; combine graphite carbon black, conductive agent, binder, fullerene, nanowire, nano Titanium is mixed to obtain a mixed negative electrode slurry;
(2)涂布：将上述正极浆料通过涂布机涂于铝箔上；将负极浆料通过涂布机涂于铜箔上；(2) Coating: coating the above-mentioned positive electrode slurry on the aluminum foil through a coating machine; coating the negative electrode slurry on the copper foil through a coating machine;
(3)然后经过辊压、分切、制片、卷绕、装配、顶侧封、烘干、注液、化成、化成，最后进行包装，获得本发明的电池。(3) After rolling, slitting, sheeting, winding, assembling, top-side sealing, drying, liquid injection, forming, forming, and finally packaging, the battery of the present invention is obtained.
本实施例提取富勒烯采用以下步骤：In this embodiment, the following steps are used to extract fullerene:
(1)在烧制陶瓷的氧化还原窑中放入一吨左右的木柴(没受污染的松木、杉木、桧木等)燃烧，24小时后在氧化还原窑的内壁中可提取附在上面的烟烬1100g；(1) Put about one ton of firewood (uncontaminated pine, cedar, cypress, etc.) into the redox kiln for burning ceramics. After 24 hours, the smoke attached to it can be extracted from the inner wall of the redox kiln. Embers 1100g;
(2)将这1100g的烟烬放入静电加载机进行静电加工可得110g的导电性富勒烯。(2) Put the 1100g of soot into an electrostatic loader for electrostatic processing to obtain 110g of conductive fullerene.
具体地，将步骤1)燃烧后获取的烟烬输入静电发生装置(即静电加载机，如图1所示，型号是GC50S‐N，入力电压为AC100V50/60Hz，最大出力电压为DC50kV(固定)，最大出力电流为20μA，消费电力为10VA，有效距离为50～250mm，接地100Ω以下。)烟烬在静电加载机内分别按照正负极性进行加载，得到带正电荷的富勒烯和带负电荷的富勒烯，然后将这些带电荷的富勒稀混合烟烬用甲苯法来精制，将精制后富勒稀烟烬按带正电荷的70％，带负电荷的30％的此例混合，即得到负极浆料中的富勒烯原料。Specifically, the smoke obtained after burning in step 1) is input into the electrostatic generator (ie, electrostatic loader, as shown in Figure 1, the model is GC50S-N, the input voltage is AC100V50/60Hz, and the maximum output voltage is DC50kV (fixed) , The maximum output current is 20μA, the power consumption is 10VA, the effective distance is 50-250mm, and the grounding is less than 100Ω.) The smoke is loaded in the electrostatic loading machine according to the positive and negative polarity to obtain positively charged fullerene and belt Negatively charged fullerenes, and then these charged fullerene mixtures are refined by the toluene method, and the refined fullerenes are 70% positively charged and 30% negatively charged. By mixing, the fullerene raw material in the negative electrode slurry is obtained.
本实施例中电解液的制备方法为：The preparation method of the electrolyte in this embodiment is:
将有机溶剂碳酸甲乙酯、碳酸二甲酯、丙酸甲酯混合，最后加入邻苯二酚二乙酸酯，添加量为电解液总体积的2％，即得所述电解液。The organic solvent ethyl methyl carbonate, dimethyl carbonate, and methyl propionate are mixed, and finally catechol diacetate is added in an amount of 2% of the total volume of the electrolyte to obtain the electrolyte.
本实施例中负极材料采用以下方法制备：将石墨碳黑、导电剂、粘合剂、富勒烯、纳米线、纳米钛混合后研磨成粉，将粉体移至压力为50mPa高压反应釜中，然后将反应釜放置在功率为1800w的微波炉中，加热1200s，冷却至室温，得到所述负极材料。In this embodiment, the negative electrode material is prepared by the following method: graphite carbon black, conductive agent, binder, fullerene, nanowire, and nano titanium are mixed and ground into powder, and the powder is moved to a high-pressure reactor with a pressure of 50 mPa , And then place the reaction kettle in a microwave oven with a power of 1800W, heat it for 1200s, and cool to room temperature to obtain the negative electrode material.
实施例2Example 2
本实施例磷酸铁锂电池，其正极材料包含以下组分：磷酸铁锂10份、导电剂30份、粘合剂15份、碳纳米管浆料30份；所述负极材料包含以下重量份的组分：石墨碳黑20份、导电剂30份、粘合剂15份、富勒烯25份、纳米线份15份、纳米钛8份，所述邻苯二酚二乙酸酯的质量分数为12％。In the lithium iron phosphate battery of this embodiment, the positive electrode material contains the following components: 10 parts of lithium iron phosphate, 30 parts of conductive agent, 15 parts of binder, and 30 parts of carbon nanotube slurry; the negative electrode material contains the following parts by weight Components: 20 parts of graphite carbon black, 30 parts of conductive agent, 15 parts of binder, 25 parts of fullerene, 15 parts of nanowires, 8 parts of nano-titanium, mass fraction of the catechol diacetate Is 12%.
本实施例磷酸铁锂电池的制备方法采用与实施例1相同的制备方法。The preparation method of the lithium iron phosphate battery in this embodiment adopts the same preparation method as in Example 1.
本实施例提取富勒烯的方法采用与实施例1相同的提取方法。The method for extracting fullerenes in this embodiment adopts the same extraction method as in Example 1.
本实施例中电解液的制备方法为：The preparation method of the electrolyte in this embodiment is:
将有机溶剂碳酸甲乙酯、碳酸二甲酯、丙酸甲酯混合，最后加入邻苯二酚二乙酸酯，添加量为电解液总体积的10％，即得所述电解液。The organic solvent ethyl methyl carbonate, dimethyl carbonate, and methyl propionate are mixed, and finally catechol diacetate is added in an amount of 10% of the total volume of the electrolyte to obtain the electrolyte.
本实施例中负极材料采用以下方法制备：将石墨碳黑、导电剂、粘合剂、富勒烯、纳米线、纳米钛混合后研磨成粉，将粉体移至压力为30mPa高压反应釜中，然后将反应釜放置在功率为2200w的微波炉中，加热200s，冷却至室温，得到所述负极材料。In this embodiment, the negative electrode material is prepared by the following method: graphite carbon black, conductive agent, binder, fullerene, nanowire, and nano titanium are mixed and ground into powder, and the powder is moved to a high pressure reactor with a pressure of 30 mPa , And then place the reaction kettle in a microwave oven with a power of 2200W, heat it for 200s, and cool to room temperature to obtain the negative electrode material.
实施例3Example 3
本实施例磷酸铁锂电池，其正极材料包含以下组分：磷酸铁锂7份、导电剂15份、粘合剂7份、碳纳米管浆料15份；所述负极材料包含以下重量份的组分：石墨碳黑10份、导电剂15份、粘合剂8份、富勒烯12份、纳米线份10份、纳米钛5份，所述邻苯二酚二乙酸酯的质量分数为10％。In the lithium iron phosphate battery of this embodiment, the positive electrode material includes the following components: 7 parts of lithium iron phosphate, 15 parts of conductive agent, 7 parts of binder, and 15 parts of carbon nanotube slurry; the negative electrode material contains the following parts by weight Components: 10 parts of graphite carbon black, 15 parts of conductive agent, 8 parts of binder, 12 parts of fullerene, 10 parts of nanowires, 5 parts of nano-titanium, mass fraction of the catechol diacetate Is 10%.
本实施例磷酸铁锂电池的制备方法采用与实施例1相同的制备方法。The preparation method of the lithium iron phosphate battery in this embodiment adopts the same preparation method as in Example 1.
本实施例富勒烯的提取方法采用与实施例1相同的提取方法。The extraction method of fullerene in this embodiment adopts the same extraction method as that in embodiment 1.
本实施例中负极材料的制备方法采用与实施例1相同的制备方法。The preparation method of the negative electrode material in this embodiment adopts the same preparation method as in Example 1.
本实施例中电解液的制备方法为：The preparation method of the electrolyte in this embodiment is:
将有机溶剂碳酸甲乙酯、碳酸二甲酯、丙酸甲酯混合，最后加入邻苯二酚二乙酸酯，添加量为电解液总体积的5％，即得所述电解液。The organic solvent ethyl methyl carbonate, dimethyl carbonate, and methyl propionate are mixed, and finally catechol diacetate is added, and the addition amount is 5% of the total volume of the electrolyte to obtain the electrolyte.
实施例4Example 4
本实施例磷酸铁锂电池，其正极材料包含以下组分：磷酸铁锂7份、导电 剂22份、粘合剂13份、石墨烯10份；所述负极材料包含以下重量份的组分：石墨碳黑12份、导电剂25份、粘合剂11份、富勒烯0.03份、纳米线8份、纳米钛3份。In the lithium iron phosphate battery of this embodiment, the positive electrode material includes the following components: 7 parts of lithium iron phosphate, 22 parts of conductive agent, 13 parts of binder, and 10 parts of graphene; the negative electrode material includes the following components by weight: Graphite carbon black 12 parts, conductive agent 25 parts, binder 11 parts, fullerene 0.03 parts, nanowires 8 parts, nano titanium 3 parts.
本实施例磷酸铁锂电池的制备方法，包括以下步骤：The preparation method of the lithium iron phosphate battery of this embodiment includes the following steps:
(1)配料：将磷酸铁锂、导电剂、粘合剂、碳纳米管浆料进行混合得到混合正极浆料；将石墨碳黑、导电剂、粘合剂、富勒烯、纳米线、纳米钛进行混合得到混合负极浆料；(1) Ingredients: mix lithium iron phosphate, conductive agent, binder, and carbon nanotube slurry to obtain mixed positive electrode slurry; combine graphite carbon black, conductive agent, binder, fullerene, nanowire, nano Titanium is mixed to obtain a mixed negative electrode slurry;
(2)涂布：将上述正极浆料通过涂布机涂于铝箔上；将负极浆料通过涂布机涂于铜箔上；(2) Coating: coating the above-mentioned positive electrode slurry on the aluminum foil through a coating machine; coating the negative electrode slurry on the copper foil through a coating machine;
(3)然后经过辊压、分切、制片、卷绕、装配、顶侧封、烘干、注液、化成、化成，最后进行包装，获得本发明的电池。(3) After rolling, slitting, sheeting, winding, assembling, top-side sealing, drying, liquid injection, forming, forming, and finally packaging, the battery of the present invention is obtained.
本实施例提取富勒烯采用以下步骤：In this embodiment, the following steps are used to extract fullerene:
①在烧制陶瓷的氧化还原窑中放入一吨没受污染的桧木柴，燃烧，燃烧充分24小时后在氧化还原窑的内壁中提取附在上面的烟烬780g；①Put one ton of uncontaminated cypress wood in the redox kiln for burning ceramics, burn it, and extract 780g of smoke attached to the inner wall of the redox kiln after 24 hours of burning;
②将提取的烟烬放入静电加载机进行静电加工，获得导电性富勒烯。② Put the extracted smoke into an electrostatic loader for electrostatic processing to obtain conductive fullerene.
需要说明的是，静电加载机意为静电产生机(Electrostatic Generator)，静电产生机可以通过处理可被燃烧物品(比如原木烧成木炭，原木是可被燃烧物品，包括矿石、圆石之类的)产生静电。It should be noted that the electrostatic loading machine means an Electrostatic Generator. The electrostatic generator can process combustible items (such as logs into charcoal, logs are combustible items, including ore, cobblestone, etc.) ) Generate static electricity.
本实施例中电解液的制备方法为：The preparation method of the electrolyte in this embodiment is:
将有机溶剂碳酸甲乙酯、碳酸二甲酯、丙酸甲酯混合，最后加入邻苯二酚二乙酸酯和锂盐，邻苯二酚二乙酸酯的添加量为电解液总体积的2％，即得所述电解液。Mix the organic solvent ethyl methyl carbonate, dimethyl carbonate, and methyl propionate, and finally add catechol diacetate and lithium salt. The addition amount of catechol diacetate is the total volume of the electrolyte 2%, the electrolyte is obtained.
本实施例中负极材料采用以下方法制备：将石墨碳黑、导电剂、粘合剂、 富勒烯、纳米线、纳米钛混合后研磨成粉，将粉体移至压力为40mPa高压反应釜中，然后将反应釜放置在功率为1900w的微波炉中，加热1000s，冷却至室温，得到所述负极材料。In this embodiment, the negative electrode material is prepared by the following method: graphite carbon black, conductive agent, binder, fullerene, nanowire, and nano titanium are mixed and ground into powder, and the powder is moved to a high pressure reactor with a pressure of 40 mPa Then, the reaction kettle was placed in a microwave oven with a power of 1900w, heated for 1000s, and cooled to room temperature to obtain the negative electrode material.
实施例5Example 5
本实施例磷酸铁锂电池，其正极材料包含以下组分：磷酸铁锂6份、导电剂15份、粘合剂8份、碳纳米管浆料10份；所述负极材料包含以下重量份的组分：石墨碳黑17份、导电剂9份、粘合剂11份、富勒烯2.5份、纳米线8份、纳米钛3份。In the lithium iron phosphate battery of this embodiment, the positive electrode material contains the following components: 6 parts of lithium iron phosphate, 15 parts of conductive agent, 8 parts of binder, and 10 parts of carbon nanotube slurry; the negative electrode material contains the following parts by weight Components: 17 parts of graphite carbon black, 9 parts of conductive agent, 11 parts of binder, 2.5 parts of fullerene, 8 parts of nanowire, 3 parts of nano titanium.
本实施例磷酸铁锂电池的制备方法，包括以下步骤：The preparation method of the lithium iron phosphate battery of this embodiment includes the following steps:
(1)配料：将磷酸铁锂、导电剂、粘合剂、碳纳米管浆料进行混合得到混合正极浆料；将石墨碳黑、导电剂、粘合剂、富勒烯、纳米线、纳米钛进行混合得到混合负极浆料；(1) Ingredients: mix lithium iron phosphate, conductive agent, binder, and carbon nanotube slurry to obtain mixed positive electrode slurry; combine graphite carbon black, conductive agent, binder, fullerene, nanowire, nano Titanium is mixed to obtain a mixed negative electrode slurry;
(2)涂布：将上述正极浆料通过涂布机涂于铝箔上；将负极浆料通过涂布机涂于铜箔上；(2) Coating: coating the above-mentioned positive electrode slurry on the aluminum foil through a coating machine; coating the negative electrode slurry on the copper foil through a coating machine;
(3)然后经过辊压、分切、制片、卷绕、装配、顶侧封、烘干、注液、化成、化成，最后进行包装，获得本发明的电池。(3) After rolling, slitting, sheeting, winding, assembling, top-side sealing, drying, liquid injection, forming, forming, and finally packaging, the battery of the present invention is obtained.
本实施例提取富勒烯采用以下步骤：In this embodiment, the following steps are used to extract fullerene:
①在烧制陶瓷的氧化还原窑中放入一吨没受污染的松木木柴，燃烧，燃烧充分24小时后在氧化还原窑的内壁中提取附在上面的烟烬1100g；①Put one ton of uncontaminated pine wood into the redox kiln for firing ceramics, burn it, and extract 1100g of smoke attached to the inner wall of the redox kiln after 24 hours of burning;
②将提取的烟烬放入静电加载机进行静电加工，获得导电性富勒烯。② Put the extracted smoke into an electrostatic loader for electrostatic processing to obtain conductive fullerene.
本实施例中电解液的制备方法为：The preparation method of the electrolyte in this embodiment is:
将有机溶剂碳酸甲乙酯、碳酸二甲酯、丙酸甲酯混合，最后加入邻苯二酚 二乙酸酯和锂盐，邻苯二酚二乙酸酯的添加量为电解液总体积的10％，即得所述电解液。Mix the organic solvent ethyl methyl carbonate, dimethyl carbonate, and methyl propionate, and finally add catechol diacetate and lithium salt. The addition amount of catechol diacetate is the total volume of the electrolyte 10%, the electrolyte is obtained.
本实施例中负极材料采用以下方法制备：将石墨碳黑、导电剂、粘合剂、富勒烯、纳米线、纳米钛混合后研磨成粉，将粉体移至压力为45mPa高压反应釜中，然后将反应釜放置在功率为2000w的微波炉中，加热700s，冷却至室温，得到所述负极材料。In this embodiment, the negative electrode material is prepared by the following method: graphite carbon black, conductive agent, binder, fullerene, nanowire, and nano titanium are mixed and ground into powder, and the powder is moved to a high-pressure reactor with a pressure of 45 mPa Then, the reaction kettle was placed in a microwave oven with a power of 2000w, heated for 700s, and cooled to room temperature to obtain the negative electrode material.
对比例1Comparative example 1
对比例1与实施例1的唯一区别是电解液中未添加邻苯二酚二乙酸酯。The only difference between Comparative Example 1 and Example 1 is that catechol diacetate is not added to the electrolyte.
对比例2Comparative example 2
对比例2与实施例1的唯一区别是负极材料中不含有富勒烯、纳米线、纳米钛。The only difference between Comparative Example 2 and Example 1 is that the negative electrode material does not contain fullerenes, nanowires, and nanometer titanium.
对比例3Comparative example 3
对比例3与实施例1的不同之处在于：负极材料中不包括富勒烯。The difference between Comparative Example 3 and Example 1 is that fullerene is not included in the negative electrode material.
将上述实施例1‐5和对比例1‐3制备的磷酸铁锂电池，进行测试，测试指标和测试结果如下所述。The lithium iron phosphate batteries prepared in the foregoing Examples 1-5 and Comparative Examples 1-3 were tested, and the test indicators and test results are as follows.
1、性能测试1. Performance test
(1)低温放电容量测试(1) Low temperature discharge capacity test
25℃下，将磷酸铁锂电池先以1C放电至2.0V；再在以1C恒流充电至3.6V，然后恒压充电至电流为0.05C，记充电容量为CC；然后将炉温调节至‐10℃，用 1C恒流放电至2.0V，记放电容量为CDT。放电容量与充电容量比即为放电容量保持率。At 25℃, discharge the lithium iron phosphate battery at 1C to 2.0V; then charge at 1C constant current to 3.6V, then charge at constant voltage to 0.05C, record the charge capacity as CC; then adjust the furnace temperature to -10℃, discharge to 2.0V with 1C constant current, record the discharge capacity as CDT. The ratio of discharge capacity to charge capacity is the discharge capacity retention rate.
磷酸铁锂电池‐10℃下的放电容量保持率(％)＝CDT/CC×100％。Lithium iron phosphate battery discharge capacity retention rate (%) at -10°C=CDT/CC×100%.
(2)常温循环测试(2) Normal temperature cycle test
25℃下，将磷酸铁锂电池先以1C放电至2.0V后进行循环测试。以1C恒流充电至3.6V，然后恒压充电至电流为0.05C，然后用1C恒流放电至2.0V，如此充电/放电，计算磷酸铁锂电池25℃下循环1000次的容量保持率。At 25°C, the lithium iron phosphate battery was first discharged to 2.0V at 1C and then subjected to a cycle test. Charge to 3.6V with a constant current of 1C, then charge with a constant voltage to a current of 0.05C, and then discharge to 2.0V with a constant current of 1C. Then charge/discharge, calculate the capacity retention rate of the lithium iron phosphate battery at 25°C for 1000 cycles.
磷酸铁锂电池25℃下循环1000次后的容量保持率(％)＝第1000次循环的放电容量/首次循环的放电容量×100％。The capacity retention rate (%) of the lithium iron phosphate battery after 1000 cycles at 25°C = the discharge capacity at the 1000th cycle/the discharge capacity at the first cycle×100%.
(3)高温循环测试(3) High temperature cycle test
25℃下，将磷酸铁锂电池先以1C放电至2.0V后进行循环测试。烘箱升温至60℃，以1C恒流充电至3.6V，然后恒压充电至电流为0.05C，然后用1C恒流放电至2.0V，如此充电/放电，计算磷酸铁锂电池60℃下循环500次的容量保持率。At 25°C, the lithium iron phosphate battery was first discharged to 2.0V at 1C and then subjected to a cycle test. The oven is heated to 60℃, charged with 1C constant current to 3.6V, then charged with constant voltage to a current of 0.05C, and then discharged with 1C constant current to 2.0V, so charge/discharge, calculate the lithium iron phosphate battery to cycle 500 at 60℃ Capacity retention rate.
磷酸铁锂电池60℃下循环500次后的容量保持率(％)＝第500次循环的放电容量/首次循环的放电容量×100％。The capacity retention rate of the lithium iron phosphate battery after 500 cycles at 60°C (%)=discharge capacity at the 500th cycle/discharge capacity at the first cycle×100%.
表1：实施例1‐3与对比例1、2的性能测试结果Table 1: Performance test results of Examples 1-3 and Comparative Examples 1 and 2
Figure PCTCN2020075052-appb-000001
Figure PCTCN2020075052-appb-000001
Figure PCTCN2020075052-appb-000002
Figure PCTCN2020075052-appb-000002
从对比例1可看出，正负极膜片压实密度提高，在不加入邻苯二酚二乙酸酯的情况下，磷酸铁锂电池的性能迅速下降，从对比例2可看出，由于负极材料中没有添加富勒烯、纳米线、纳米钛，使得对比例2‐3的磷酸铁锂电池负极膜片压实密度远低于本发的实施例。但是在实施例1‐5中，正负极膜片压实密度提高，且在电解液中加入邻苯二酚二乙酸酯后可以明显延缓磷酸铁锂电池的性能下降趋势，使磷酸铁锂电池的低温性能、常温和高温循环性能都得到改善。这说明加入的邻苯二酚二乙酸酯可以延长磷酸铁锂电池的循环使用寿命。It can be seen from Comparative Example 1 that the compaction density of the positive and negative electrode membranes is increased, and the performance of the lithium iron phosphate battery drops rapidly without adding catechol diacetate. From Comparative Example 2, it can be seen that Since fullerenes, nanowires, and nano-titanium are not added to the negative electrode material, the compaction density of the negative electrode membrane of the lithium iron phosphate battery of Comparative Examples 2-3 is much lower than the embodiment of the present invention. However, in Examples 1-5, the compaction density of the positive and negative electrodes is increased, and the addition of catechol diacetate in the electrolyte can significantly delay the decline in the performance of the lithium iron phosphate battery, so that the lithium iron phosphate The low temperature performance, normal temperature and high temperature cycle performance of the battery are all improved. This shows that the added catechol diacetate can extend the cycle life of the lithium iron phosphate battery.
2、破坏性测试结果2. Destructive test results
取实施例1‐5获取的磷酸铁锂电池(规格均为25×37×76mm)进行破坏性测试。Take the lithium iron phosphate batteries (all 25×37×76 mm in size) obtained in Examples 1-5 for destructive testing.
(1)锤击测试：10kg重的钢锤在1米高度自然落下：不起火、不爆炸；(1) Hammer test: a 10kg steel hammer falls naturally at a height of 1 meter: no fire, no explosion;
(2)过充测试：不会发热、不爆炸；(2) Overcharge test: no heat or explosion;
(3)钉刺测试：用3×8.0mm的铁钉直接钉穿电池，不起火、不爆炸；(3) Nail penetration test: Use 3×8.0mm iron nails to directly penetrate the battery without fire or explosion;
(4)浸水测试：24小时浸水，性能不变；(4) Water immersion test: 24 hours water immersion, the performance remains unchanged;
(5)耐热冲击测试：放入温度测试箱中，将温度从5℃升到150℃，不起火、不爆炸；(5) Thermal shock test: Put it in a temperature test box and raise the temperature from 5°C to 150°C without fire or explosion;
(6)振动测试：放于振动测试机中，往復振动30分钟，外观、性能不变；(6) Vibration test: Put it in a vibration tester and vibrate back and forth for 30 minutes, the appearance and performance remain unchanged;
(7)挤压测试：放于挤压机中，施加最大17MPa的压力，不起火、不爆炸；(7) Extrusion test: Put it in an extruder and apply a maximum pressure of 17 MPa, without fire or explosion;
(8)螺丝刀贯穿测试：螺丝刀贯穿电池后，电压不变化(一般电池会因贯穿造成短路、电压为零)，6‐7分钟后有6‐7°的升温；(8) Screwdriver penetration test: After the screwdriver penetrates the battery, the voltage does not change (generally the battery will be short-circuited and the voltage is zero due to penetration), and there will be a 6-7° heating up after 6-7 minutes;
(9)落下测试：将电池放于6米高度自然落下在铁板上，电压不变。(9) Drop test: Put the battery at a height of 6 meters and drop it naturally on the iron plate, the voltage does not change.
通过以上实验证实，本发明实施例1‐5的磷酸铁锂电池质量完全符合PSE、GB、UC等安全认证要求。It is confirmed by the above experiments that the quality of the lithium iron phosphate battery of the embodiments 1 to 5 of the present invention fully meets the safety certification requirements of PSE, GB, UC, etc.
以上所述实施例仅表达了本发明的几种实施方式，其描述较为具体和详细，但并不能因此而理解为对发明专利范围的限制。应当指出的是，对于本领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干变形和改进，这些都属于本发明的保护范围。因此，本发明专利的保护范围应以所附权利要求为准。The above-mentioned embodiments only express several embodiments of the present invention, and the descriptions are more specific and detailed, but they should not be understood as limiting the scope of the invention patent. It should be pointed out that for those of ordinary skill in the art, without departing from the concept of the present invention, several modifications and improvements can be made, and these all fall within the protection scope of the present invention. Therefore, the protection scope of the patent of the present invention should be subject to the appended claims.

Claims (10)

  1. 一种磷酸铁锂电池，其特征在于，所述磷酸铁锂电池的正极材料包含以下组分：磷酸铁锂、导电剂、粘合剂、碳纳米管浆料或石墨烯；负极材料包含以下组分：石墨碳黑、导电剂、粘合剂、富勒烯、纳米线、纳米钛；以及电解液，电解液包括邻苯二酚二乙酸酯。A lithium iron phosphate battery, characterized in that the positive electrode material of the lithium iron phosphate battery comprises the following components: lithium iron phosphate, conductive agent, binder, carbon nanotube slurry or graphene; the negative electrode material comprises the following components Points: graphite carbon black, conductive agent, adhesive, fullerene, nanowire, nano titanium; and electrolyte, which includes catechol diacetate.
  2. 如权利要求1所述的磷酸铁锂电池，其特征在于，所述正极材料包含以下重量份的组分：磷酸铁锂2-10份、导电剂5-30份、粘合剂1-15份、碳纳米管浆料或石墨烯2.5-30份；所述负极材料包含以下重量份的组分：石墨碳黑1-20份、导电剂5-30份、粘合剂1-15份、富勒烯0.8-25份、纳米线5-15份、纳米钛2-8份，所述邻苯二酚二乙酸酯的质量分数为5-12％。The lithium iron phosphate battery according to claim 1, wherein the positive electrode material comprises the following components by weight: 2-10 parts of lithium iron phosphate, 5-30 parts of conductive agent, 1-15 parts of binder , Carbon nanotube slurry or graphene 2.5-30 parts; the negative electrode material contains the following components by weight: graphite carbon black 1-20 parts, conductive agent 5-30 parts, binder 1-15 parts, rich 0.8-25 parts of Leene, 5-15 parts of nanowires, 2-8 parts of nano titanium, and the mass fraction of catechol diacetate is 5-12%.
  3. 如权利要求1或2所述的磷酸铁锂电池，其特征在于，所述正极为铝箔；所述负极为铜箔。The lithium iron phosphate battery according to claim 1 or 2, wherein the positive electrode is aluminum foil; and the negative electrode is copper foil.
  4. 如权利要求1或2所述的磷酸铁锂电池，其特征在于，所述富勒烯由70％带正电荷的富勒烯和30％带负电荷的富勒烯制备而成。The lithium iron phosphate battery according to claim 1 or 2, wherein the fullerene is prepared from 70% positively charged fullerene and 30% negatively charged fullerene.
  5. 如权利要求1或2所述的磷酸铁锂电池，其特征在于，所述导电剂为乙炔黑。The lithium iron phosphate battery of claim 1 or 2, wherein the conductive agent is acetylene black.
  6. 如权利要求1或2所述的磷酸铁锂电池，其特征在于，所述粘合剂为聚偏氟乙烯。The lithium iron phosphate battery according to claim 1 or 2, wherein the binder is polyvinylidene fluoride.
  7. 一种制备如权利要求1-6所述的磷酸铁锂电池的制备方法，其特征在于，包括以下步骤：A method for preparing the lithium iron phosphate battery according to claims 1-6, characterized by comprising the following steps:
    (1)配料：将磷酸铁锂、导电剂、粘合剂、碳纳米管浆料进行混合得到混合正极浆料；将石墨碳黑、导电剂、粘合剂、富勒烯、纳米线、纳米钛进行混合得到混合负极浆料；(1) Ingredients: mix lithium iron phosphate, conductive agent, binder, and carbon nanotube slurry to obtain mixed positive electrode slurry; combine graphite carbon black, conductive agent, binder, fullerene, nanowire, nano Titanium is mixed to obtain a mixed negative electrode slurry;
    (2)涂布：将上述正极浆料通过涂布机涂于正极上；将负极浆料通过涂 布机涂于负极上；(2) Coating: apply the above-mentioned positive electrode slurry on the positive electrode through a coater; apply the negative electrode slurry on the negative electrode through a coater;
    (3)然后经过辊压、分切、制片、卷绕、装配、顶侧封、烘干、注入电解液、化成，最后进行包装，获得本发明的电池。(3) After rolling, slitting, sheeting, winding, assembling, top-side sealing, drying, electrolyte injection, forming, and finally packaging, the battery of the present invention is obtained.
  8. 如权利要求7所述的磷酸铁锂电池的制备方法，其特征在于，所述步骤(1)之前还需提取富勒烯，其提取方法采用以下步骤：将碳粉放入氧化还原釜通电燃烧，然后提取附在釜内壁的碳气黑微粒，再通过静电加工即得所述富勒烯。The method for preparing a lithium iron phosphate battery according to claim 7, wherein the fullerene needs to be extracted before the step (1), and the extraction method adopts the following steps: put the carbon powder into the redox kettle and energize and burn Then, the carbon black particles attached to the inner wall of the kettle are extracted, and then the fullerene is obtained by electrostatic processing.
  9. 如权利要求7所述的磷酸铁锂电池的制备方法，其特征在于，所述步骤(1)之前还需制备电解液，采用以下方法制备：将有机溶剂碳酸甲乙酯、碳酸二甲酯、丙酸甲酯混合，最后加入邻苯二酚二乙酸酯，添加量为电解液总体积的2～10％，即得所述电解液。The method for preparing a lithium iron phosphate battery according to claim 7, characterized in that, before the step (1), an electrolyte needs to be prepared, which is prepared by the following method: the organic solvent ethyl methyl carbonate, dimethyl carbonate, Methyl propionate is mixed, and finally catechol diacetate is added, and the addition amount is 2-10% of the total volume of the electrolyte to obtain the electrolyte.
  10. 如权利要求7所述的磷酸铁锂电池的制备方法，其特征在于，所述步骤(2)负极材料采用以下方法制备：将石墨碳黑、导电剂、粘合剂、富勒烯、纳米线、纳米钛混合后研磨成粉，将粉体移至压力为30～50mPa高压反应釜中，然后将反应釜放置在功率为1800～2200w的微波炉中，加热200～1200s，冷却至室温，得到所述负极材料。The method for preparing a lithium iron phosphate battery according to claim 7, wherein the step (2) of the negative electrode material is prepared by the following method: graphite carbon black, conductive agent, binder, fullerene, nanowire , Nano-titanium is mixed and ground into powder, the powder is moved to a 30-50mPa autoclave, and then the reactor is placed in a microwave oven with a power of 1800-2200w, heated for 200-1200s, cooled to room temperature, and obtained Mentioned negative electrode material.
PCT/CN2020/075052 2019-02-22 2020-02-13 Lithium iron phosphate battery and preparation method therefor WO2020168974A1 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
JP2021547314A JP2022527237A (en) 2019-02-22 2020-02-13 Lithium iron phosphate battery and its preparation method
KR1020217030181A KR20210148121A (en) 2019-02-22 2020-02-13 Lithium iron phosphate battery and manufacturing method thereof

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201910134277.6 2019-02-22
CN201910134277.6A CN111584925B (en) 2019-02-22 2019-02-22 Lithium iron phosphate battery and preparation method thereof

Publications (1)

Publication Number Publication Date
WO2020168974A1 true WO2020168974A1 (en) 2020-08-27

Family

ID=72124347

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2020/075052 WO2020168974A1 (en) 2019-02-22 2020-02-13 Lithium iron phosphate battery and preparation method therefor

Country Status (4)

Country Link
JP (1) JP2022527237A (en)
KR (1) KR20210148121A (en)
CN (1) CN111584925B (en)
WO (1) WO2020168974A1 (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113809387A (en) * 2021-08-16 2021-12-17 福建巨电新能源股份有限公司 Lithium iron phosphate lithium battery
CN114373933A (en) * 2022-01-07 2022-04-19 北京胜能能源科技有限公司 Solid-state battery positive plate and preparation method thereof and solid-state battery
CN115072687A (en) * 2022-07-28 2022-09-20 四川龙蟒磷化工有限公司 Method for preparing battery-grade iron phosphate by using sulfuric acid cinder

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103403928A (en) * 2011-03-08 2013-11-20 日产自动车株式会社 Negative electrode active material for electrical devices
CN104471761A (en) * 2012-05-07 2015-03-25 古河电气工业株式会社 Negative electrode for nonaqueous electrolyte rechargeable battery and nonaqueous electrolyte rechargeable battery using same

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106784812A (en) * 2016-11-21 2017-05-31 深圳市沃特玛电池有限公司 A kind of preparation method of ferric phosphate lithium cell
CN109119686B (en) * 2017-06-23 2020-11-20 宁德时代新能源科技股份有限公司 Lithium iron phosphate battery
CN107978728A (en) * 2017-10-31 2018-05-01 旭成（福建）科技股份有限公司 A kind of lithium ion battery coating material and coating method
CN108615955B (en) * 2018-05-07 2020-08-28 深圳市壹绿通环保资源有限公司 Formation method of lithium iron phosphate battery
CN108847478A (en) * 2018-06-04 2018-11-20 安徽潜川动力锂电科技有限公司 A kind of lithium battery silicon-carbon nano composite anode material and preparation method thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103403928A (en) * 2011-03-08 2013-11-20 日产自动车株式会社 Negative electrode active material for electrical devices
CN104471761A (en) * 2012-05-07 2015-03-25 古河电气工业株式会社 Negative electrode for nonaqueous electrolyte rechargeable battery and nonaqueous electrolyte rechargeable battery using same

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113809387A (en) * 2021-08-16 2021-12-17 福建巨电新能源股份有限公司 Lithium iron phosphate lithium battery
CN113809387B (en) * 2021-08-16 2023-03-24 福建巨电新能源股份有限公司 Lithium iron phosphate lithium battery
CN114373933A (en) * 2022-01-07 2022-04-19 北京胜能能源科技有限公司 Solid-state battery positive plate and preparation method thereof and solid-state battery
CN114373933B (en) * 2022-01-07 2023-11-21 北京胜能能源科技有限公司 Solid-state battery positive plate, preparation method thereof and solid-state battery
CN115072687A (en) * 2022-07-28 2022-09-20 四川龙蟒磷化工有限公司 Method for preparing battery-grade iron phosphate by using sulfuric acid cinder
CN115072687B (en) * 2022-07-28 2023-09-01 四川龙蟒磷化工有限公司 Method for preparing battery-grade ferric phosphate by using sulfuric acid cinder

Also Published As

Publication number Publication date
CN111584925A (en) 2020-08-25
KR20210148121A (en) 2021-12-07
JP2022527237A (en) 2022-06-01
CN111584925B (en) 2021-11-05

Similar Documents

Publication Publication Date Title
WO2020168974A1 (en) Lithium iron phosphate battery and preparation method therefor
CN104143635B (en) A kind of artificial plumbago negative pole material and preparation method thereof
CN103887502B (en) A kind of Delanium lithium ion battery negative material and preparation method thereof
CN101533900B (en) Phosphorus composite material used for electrochemistry reversible lithium storage and preparation method thereof
CN102593434B (en) Composite graphite particles for lithium secondary battery and preparation method thereof
WO2016201940A1 (en) Preparation method for carbon/graphite composite anode material
CN104779372A (en) Cyclic utilization method for using graphite fine powder as negative pole material of lithium-ion batteries
CN104143641B (en) A kind of interphase negative material and preparation method thereof
CN111370654B (en) Composite graphite negative electrode material, lithium ion battery and preparation method and application thereof
CN102485648A (en) Modified graphite, composite graphite material containing the modified graphite and their preparation methods and application
CN104409698B (en) A kind of composite lithium ion battery cathode material and preparation method thereof
CN106505199B (en) A kind of composite cathode material for lithium ion cell and preparation method thereof, lithium ion battery
CN104300120A (en) Hydrothermal synthesis method of nano-lithium titanate material
CN102593444A (en) Preparation method of carbon-coated lithium titanate and product of carbon-coated lithium titanate
CN104300148B (en) A kind of graphite negative material of lithium ion battery and preparation method thereof
CN114613974A (en) Long-life quick-charging type lithium ion battery cathode material and preparation method thereof
CN104916844A (en) Method using artificial graphite fine powder subjected to doping processing as anode material
WO2020168973A1 (en) Carbon nanotube fullerene battery and preparation method therefor
WO2020168975A1 (en) Lithium polymer battery and preparation method therefor
CN104766964A (en) Method for using natural graphite fine powder as negative pole material by doping treatment
CN102255071A (en) Modified graphite material as well as manufacturing method and application thereof
CN110429272A (en) The silicon-carbon composite cathode material and preparation method thereof of one type dragon fruit structure
CN109920982A (en) A kind of lithium ion battery silicon-carbon cathode material and preparation method
CN104953116B (en) Method for preparing LiYO2 battery material
CN111232970B (en) Graphite negative electrode material, lithium ion battery, preparation method and application

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: 20759304

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2021547314

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 20759304

Country of ref document: EP

Kind code of ref document: A1