CN113540410A - Preparation method and application of lithium iron phosphate cathode material synthesized by rapid high-temperature thermal shock method - Google Patents

Preparation method and application of lithium iron phosphate cathode material synthesized by rapid high-temperature thermal shock method Download PDF

Info

Publication number
CN113540410A
CN113540410A CN202110784512.1A CN202110784512A CN113540410A CN 113540410 A CN113540410 A CN 113540410A CN 202110784512 A CN202110784512 A CN 202110784512A CN 113540410 A CN113540410 A CN 113540410A
Authority
CN
China
Prior art keywords
lifepo
precursor
preparation
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
CN202110784512.1A
Other languages
Chinese (zh)
Inventor
陈亚楠
许运华
罗佳薇
曾翠华
朱伟
张景超
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.)
Tianjin University
Original Assignee
Tianjin University
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 Tianjin University filed Critical Tianjin University
Priority to CN202110784512.1A priority Critical patent/CN113540410A/en
Publication of CN113540410A publication Critical patent/CN113540410A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • 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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/136—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
    • H01M4/1397—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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • 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

Abstract

The invention provides a method for synthesizing lithium iron phosphate LiFePO by a rapid high-temperature thermal impact method4A preparation method and application of the anode material. Preparation of LiFePO by the Sol-gel method4Precursor, then carrying out rapid high-temperature thermal shock on the precursor, and finally synthesizing LiFePO4And (3) a positive electrode material. The process can shorten the dozens of hours required by the sintering of the traditional tube furnace to more than twenty seconds, and the time cost and the energy cost are both greatly reduced. And the LiFePO synthesized by the invention4The positive electrode material has good crystal form, no impurity phase and fine particles. Meanwhile, the electrochemical performance is good, and the discharge specific capacity can reach 130mAh/g at 0.1 ℃.

Description

Preparation method and application of lithium iron phosphate cathode material synthesized by rapid high-temperature thermal shock method
Technical Field
The invention relates to the technical field of lithium ion battery production, in particular to a preparation method and application of a lithium iron phosphate anode material synthesized by a rapid high-temperature thermal impact method.
Background
Nowadays, the worldwide demand for energy is increasing day by day, and the acquisition of energy is mainly realized by the consumption of fossil fuel. But resources such as petroleum, coal, natural gas, etc. are increasingly exhausted. And the acid rain, greenhouse effect and the like generated by the combustion of fossil fuel can also seriously harm our living environment. Lithium ion batteries are referred to as "green energy" because they are environmentally friendly. Lithium ion batteries have been currently developed for a new high and new technology industry. Lithium ion batteries gradually show great advantages in application, and are widely used in electronic devices such as mobile phones and notebook computers. The system comprises the fields of electric automobiles, electric bicycles, large-scale energy storage power stations, smart power grids and the like. In particular to the development and application of new energy automobiles.
Lithium ion batteries are generally composed of positive electrode materials, negative electrode materials, separators, electrolytes, and battery cases. The positive electrode material is used as an important component of the whole battery, and directly influences the service performance and the manufacturing cost of the battery. The anode material commonly used at present is LiFePO4Lithium cobaltate, lithium manganate, ternary materials and the like. Wherein LiFePO4The application is the most extensive.
LiFePO4Is an orthophosphate with an orthorhombic lattice, which is of the olivine type. The Fe atom occupies the octahedral (4c) position, and the P atom occupies the tetrahedral (4c) position. Li+Occupies the octahedral (4a) position. In the process of removing Li, Li+FePO formed after stripping4Still this crystalline structure. The formed LiFePO is formed because the oxygen atoms are tightly bonded to the iron atoms and the phosphorus atoms4The structure of (A) has better stability at high temperature. This higher lattice stability allows for LiFePO4Has good cycle performance and safety. And the material has the characteristics of no toxicity, no pollution, good safety performance and the like.
LiFePO at present4Precursor bodyThe synthesis method mainly comprises the following steps: high temperature solid phase method, carbothermic method, microwave synthesis method, ball milling method, liquid phase coprecipitation method, sol-gel method, hydrothermal synthesis method, etc. The conventional lithium iron phosphate prepared by a high-temperature solid-phase method is not uniform in size, and ferrous iron is easily oxidized into ferric iron in the synthesis process, so that impurities are generated. The microwave synthesis method has excessive energy consumption and the synthesis process is difficult to control. The hydrothermal synthesis method requires high-temperature and high-pressure equipment, and has high requirements on the equipment. And the required cathode material can be obtained after the precursor is prepared and generally needs to be calcined for tens of hours at a higher temperature, so that the consumed time cost and the energy cost are higher. Further, LiFePO synthesized by industrial method4The positive electrode material has large particle size, which causes the lithium iron phosphate material to have small specific surface area and poor rate capability.
Therefore, the invention is very beneficial to the synthesis method of the lithium iron phosphate anode material, which has simple synthesis process and can efficiently utilize time and energy.
Disclosure of Invention
The invention overcomes the defect of LiFePO4The defects of the existing preparation method of the anode material provide a preparation method and application of a LiFePO4 anode material synthesized by a rapid high-temperature thermal impact method.
Conventional LiFePO4The anode material needs to be subjected to long-time tubular furnace calcination treatment after the precursor preparation is completed. LiFePO obtained by ball milling, as described in some of the literature4The precursor is calcined for 20 hours at the temperature of 700 ℃ to obtain the battery anode material for industrial production. This calcination process requires significant time and energy costs. The invention utilizes a sol-gel method to prepare a lithium iron phosphate precursor, the precursor powder is rapidly heated and heated by the Joule heat generated by a direct current power supply, the crystal powder generates a series of reactions under the rapid thermal shock, and finally LiFePO with good electrochemical performance can be obtained4And (3) a positive electrode material. Compared with the traditional tube furnace calcination, the method can effectively reduce various costs in the production process.
The invention also overcomes the traditionLiFePO is prepared by industrial technology4The anode material has the defect of large particles, and the LiFePO prepared by the method4The positive electrode material particles are between dozens of nanometers and hundreds of nanometers, and are expected to be widely applied to rate cells.
The purpose of the invention is realized by the following scheme: preparation of LiFePO by sol-gel method4And (3) precursor. In inert gas, the obtained precursor is subjected to Joule heating calcination to synthesize LiFePO4And (3) a positive electrode material.
The preparation of LiFePO by the sol-gel method4The precursor specifically comprises:
firstly, according to the following steps of 1: 3: 1: 0.4 molar ratio of FePO4·2H2O (providing iron source and phosphate radical), H2C2O4·2H2O (as complexing agent), LiOH. H2O (providing a lithium source), glucose (as a carbon source). Then dissolved in 100-200ml of ultrapure water. After the dissolution is finished, the three-neck flask is put into an oil bath pan with the temperature of 85-95 ℃ for heating, and FePO is firstly put into4·2H2The O solution was poured into a three-necked flask, and H was titrated therein2C2O4·2H2And (3) stirring the solution O at a constant speed in the titration process. After the titration is finished, LiOH & H is added2The mixed solution of O and glucose was further titrated into a three-necked flask. The whole titration process the mixture was kept under heating and stirring in an oil bath at 85-95 deg.C until a gel was formed. Finally, the powder is put into a blast oven with the temperature of 85-95 ℃ for drying, and the dried powder is ground to obtain LiFePO4And (3) precursor powder.
The joule heating calcination process is performed under an inert atmosphere, and the inert gas may be argon or nitrogen. The amount of the precursor during calcination is 100-200 mg. The rapid high-temperature thermal shock takes carbon cloth as a carrier, and the size of the carrier is 10-20cm2. The precursor prepared by the sol-gel method is electrified with a current of 14-18A and the duration time is 15-35 s. Prepared LiFePO4Has good crystal form (pure phase of lithium iron phosphate, no other mixed phase). The particles are fine and uniformly dispersed, and have better electrochemical performance, and the discharge specific capacity of the material can reach 130mAhg-1。
Compared with the prior art, the invention has the following advantages:
the sol-gel method for preparing the precursor is combined with the high-temperature rapid thermal shock process to synthesize LiFePO4The anode material is synthesized in a mode of shortening the traditional calcination time of more than 20 hours to more than 20 seconds, so that the total time required by the whole process is greatly reduced, the synthesis process is simpler, the requirement on equipment is lower, and the LiFePO is reduced4The production cost of the cathode material in industry makes the cathode material more generally applicable. In addition, the time is reduced, the energy loss in the process is greatly reduced, and energy can be better saved and the environment can be better protected. LiFePO synthesized by the method4Has good crystal form and electrochemical performance. In conclusion, the research work provides a brand new method for preparing the positive electrode material of the lithium iron phosphate battery.
Drawings
FIG. 1 shows LiFePO prepared by the sol-gel method of the present invention4Thermally shocking the precursor under different current conditions (different temperatures) to form an XRD (X-ray diffraction) pattern of the sample;
FIG. 2 shows LiFePO prepared by the sol-gel method of the present invention4Scanning electron microscopy of the precursor under thermal shock conditions of 20V 16a 25 s. (a) A scanning electron microscope image at 2000 times magnification, and (b) a scanning electron microscope image at 40000 times magnification.
FIG. 3 shows LiFePO prepared by the sol-gel method of the present invention4And (3) a charge-discharge curve diagram of the precursor under the thermal shock condition of 20V 16A 25 s.
Detailed Description
The technical solution of the present invention is further illustrated by the following specific examples.
Step 1, LiFePO4Preparing a precursor;
preparation of LiFePO by sol-gel method4Precursor body
The whole process for preparing the precursor by sol-gel is specifically operated as follows, firstly according to the formula 1: 3: 1: 0.4 9.4369g of FePO were weighed out4·2H2O, 19.1015g of H2C2O4·2H2O, 2.1192g of LiOH. H2O, and 3.6032g of glucose. Then FePO is respectively added4·2H2O、H2C2O4·2H2O、LiOH·H2The mixture of O and glucose was dissolved in 100ml, 200ml and 100ml of ultrapure water, respectively.
In industrial processes, generally according to LiFePO4Doping a carbon source with the content of 5-10 mol%; in the fast-firing system of the present application, the carbon content is in terms of LiFePO4The proportion is the optimal proportion with better electrochemical performance obtained after experimental exploration. Due to pure LiFePO4Is poor in electronic conductivity and ionic conductivity, so that LiFePO is improved4Specific capacity, rate capability and cycle life, to which carbon addition is the most effective way. Carbon is mainly added with LiFePO4The electronic conductivity of the particle surface allows the active material to be fully utilized at higher currents. Carbon can also reduce LiFePO by inhibiting particle growth during fast firing4Particle size of (2), shortening Li in charge and discharge process+Indirectly improve the LiFePO4The rate capability of (2). In addition, carbon may act as a reductant to suppress Fe during the flash firing process of the present application2+Oxidation to Fe3+Thereby simplifying the requirements for atmosphere in the synthesis process. However, the amount of carbon is also increased in a certain proportion, and an excessively high carbon content will instead reduce its capacity, because carbon is inert and LiFePO4Too large a thickness of the carbon film coated on the surface of the particles may reduce the diffusion rate of lithium ions through the carbon film, limiting the effective utilization of the internal active material, thereby reducing the capacity. The selection of an appropriate carbon content has a great influence on the electrochemical performance thereof.
The dissolved FePO4·2H2The O solution was poured into a three-necked flask heated in a 90 ℃ oil bath. Then titrate H into it2C2O4·2H2And (3) stirring the solution O at a constant speed in the titration process. After the titration is finished, LiOH & H is added2Continuing the mixed solution of O and glucoseTitration was performed in a three-neck flask.
After all solutions were titrated, the mixture was stirred in an oil bath at 90 ℃ until a gel was formed. And finally, putting the mixture into a blowing oven at 90 ℃ for drying for 12h, and taking out the dried mixture. Grinding the dried powder to obtain LiFePO4And (3) precursor powder.
And 2, cutting 5 multiplied by 2.5cm carbon cloth as a carrier. The sample and the experimental set-up were placed in a glove box filled with inert gas (argon) (due to Fe)2+Can be oxidized into Fe when being combusted in air3+Therefore, the subsequent whole thermal shock process needs to be carried out under the protection of inert gas), and carbon cloth is taken as a carrier to carry out rapid thermal shock, and the dosage of each thermal shock is 160 mg. The thermal shock process is realized by electrifying, the electrifying current of the precursor prepared by the sol-gel method is 16A, the duration is 25s, the rapid thermal shock process is a very rapid heating and quenching process, the reaction can be rapidly carried out, and finally LiFePO can be obtained4a/C powder.
And 3, installing the button cell to judge the electrochemical performance of the button cell. Super P, PVDF 900, and the sample were weighed in a certain ratio and mixed with a certain amount of NMP (1-methyl-2-pyrrolidone). Stirring for 2-3h on a magnetic stirrer to obtain the battery slurry. Coating the aluminum foil with the coating solution, and drying in vacuum to obtain the battery pole piece. And assembling the button cell and testing the electrochemical performance of the button cell.
As shown in FIG. 1, LiFePO prepared by the sol-gel method is shown4And (3) comparing XRD patterns of the precursor after heating under different current conditions. As can be seen from the figure, the main diffraction peaks of the 3 samples are similar to those of olivine-type LiFePO4PDF card (NO.83-2092) is corresponding to the standard, and no other obvious impurity peaks are observed, which indicates that the method prepares purer LiFePO4And (3) a positive electrode material. However, the intensity of the diffraction peak is different with the increase of the current, wherein the sample obtained by calcining under the condition of 16A has the sharpest diffraction peak, the sample has the best crystallinity, and the crystal form is the most complete. From this figure it can be seen that the characteristic peak of the sample becomes increasingly apparent as the current increases, but as the current continues to increaseLarge, above a certain critical value, the intensity of the characteristic peak of the sample decreases, probably due to the fact that the grains grow faster at high temperature under the same time conditions, thus leading to LiFePO4The crystal grains become coarse.
FIG. 2(a) shows LiFePO prepared by the sol-gel method of the present invention4Scanning Electron Microscope (SEM) images of the finished product formed after thermal shock of the precursor at a magnification of 2000. It can be seen from the figure that the finished product formed after the thermal shock is lamellar and spheroidal particles, and the particles are dispersed more uniformly.
FIG. 2(b) shows LiFePO prepared by the sol-gel method according to the present invention4Scanning Electron Microscope (SEM) images of the finished product formed after thermal shock of the precursor at a magnification of 40000. . According to the graph, the obtained sample particle size is about 100-200nm, and the particles are finer.
In order to better explore the LiFePO produced by the rapid high-temperature thermal shock method4The anode material is used for judging the rationality and feasibility of the method, and the electrochemical performance of the anode material is tested.
FIG. 3 shows LiFePO prepared by the sol-gel method of the present invention4Charge and discharge curves of the samples formed after thermal shock of the precursor at 20V 16a 25 s. The curve shows that the discharge specific capacity of the lithium iron phosphate anode material synthesized by the rapid high-temperature thermal impact method can reach 130mAhg-1And LiFePO appears in the charging and discharging curve4Distinct voltage plateau (3.45V vs. li)+/Li), the electrochemical reaction can be expressed as: FePO4+XLi++Xe-→Li1-XFePO4This is typical of LiFePO4Two-phase transformation characteristics, indicating that the purity of the synthesized sample is higher.
The invention has been described in an illustrative manner, and it is to be understood that any simple variations, modifications or other equivalent changes which can be made by one skilled in the art without departing from the spirit of the invention fall within the scope of the invention.

Claims (4)

1. A preparation method for synthesizing a lithium iron phosphate anode material by a rapid high-temperature thermal shock method is characterized by comprising the following steps:
step 1, preparing LiFePO by using sol-gel method4A precursor;
0.05 molar part of FePO4·2H2O in water to give solution A, 0.15 molar part of H2C2O4·2H2O was dissolved in water to obtain a solution B, and 0.05 molar part of LiOH. H was added2Dissolving O and 0.02 molar part of glucose in water to obtain a solution C;
dripping the solution B into the solution A, and stirring at a constant speed in the dripping process; after the dripping is finished, dripping the solution C; heating and stirring at 85-95 ℃ in the whole titration process, and stirring until gel is formed after titration is finished; finally, the powder is placed into a blast oven for drying, and the dried powder is ground to obtain LiFePO4a/C precursor powder;
step 2, in an inert atmosphere, the LiFePO obtained in the step 14Placing the precursor on carbon cloth, connecting with a direct current power supply, and electrifying for 14-18A for 15-35 s; thus obtaining LiFePO4And (3) a positive electrode material.
2. The preparation method for synthesizing the lithium iron phosphate cathode material by the rapid high-temperature thermal impact method according to claim 1, wherein the drying temperature is 85-95 ℃ and the drying time is 8-16 h.
3. The method for preparing a lithium iron phosphate positive electrode material by a rapid high-temperature thermal impact method according to claim 1, wherein in the step 2, the inert atmosphere is argon.
4. The application of the lithium iron phosphate cathode material prepared by the preparation method according to any one of claims 1 to 3 in the production of lithium ion batteries.
CN202110784512.1A 2021-07-12 2021-07-12 Preparation method and application of lithium iron phosphate cathode material synthesized by rapid high-temperature thermal shock method Pending CN113540410A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202110784512.1A CN113540410A (en) 2021-07-12 2021-07-12 Preparation method and application of lithium iron phosphate cathode material synthesized by rapid high-temperature thermal shock method

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202110784512.1A CN113540410A (en) 2021-07-12 2021-07-12 Preparation method and application of lithium iron phosphate cathode material synthesized by rapid high-temperature thermal shock method

Publications (1)

Publication Number Publication Date
CN113540410A true CN113540410A (en) 2021-10-22

Family

ID=78098593

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202110784512.1A Pending CN113540410A (en) 2021-07-12 2021-07-12 Preparation method and application of lithium iron phosphate cathode material synthesized by rapid high-temperature thermal shock method

Country Status (1)

Country Link
CN (1) CN113540410A (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115650199A (en) * 2022-11-14 2023-01-31 中碳国际新能源科技(天津)有限公司 Rapid high-temperature thermal shock method for synthesizing phosphoric acid method for preparing vanadium sodium/carbon anode composite material
CN115744866A (en) * 2022-09-06 2023-03-07 天津大学 Vanadium sodium fluorophosphate material synthesized by instantaneous Joule heat sintering and preparation method and application thereof

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103367717A (en) * 2013-07-01 2013-10-23 华中科技大学 Preparation method of lithium-ion battery positive material LiFePO4/C composite material and product obtained by preparation method
CN104409734A (en) * 2014-12-26 2015-03-11 北京化工大学 Lithium iron phosphate battery positive material prepared by using microwave-assisted sol-gel method
CN105244481A (en) * 2015-09-02 2016-01-13 武汉理工力强能源有限公司 Lithium iron phosphate cathode material with carbon coating in situ and preparation method thereof
CN105552370A (en) * 2016-02-24 2016-05-04 苏州太阳源纳米科技有限公司 Spherical cathode material for lithium-ion secondary battery and preparation method of spherical cathode material
CN108963280A (en) * 2018-07-11 2018-12-07 武汉科技大学 The method for preparing carbon-based elctro-catalyst is pyrolyzed based on Joule heat

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103367717A (en) * 2013-07-01 2013-10-23 华中科技大学 Preparation method of lithium-ion battery positive material LiFePO4/C composite material and product obtained by preparation method
CN104409734A (en) * 2014-12-26 2015-03-11 北京化工大学 Lithium iron phosphate battery positive material prepared by using microwave-assisted sol-gel method
CN105244481A (en) * 2015-09-02 2016-01-13 武汉理工力强能源有限公司 Lithium iron phosphate cathode material with carbon coating in situ and preparation method thereof
CN105552370A (en) * 2016-02-24 2016-05-04 苏州太阳源纳米科技有限公司 Spherical cathode material for lithium-ion secondary battery and preparation method of spherical cathode material
CN108963280A (en) * 2018-07-11 2018-12-07 武汉科技大学 The method for preparing carbon-based elctro-catalyst is pyrolyzed based on Joule heat

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
李超等: "磷酸铁锂前驱体磷酸铁的研究进展", 《广州化工》 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115744866A (en) * 2022-09-06 2023-03-07 天津大学 Vanadium sodium fluorophosphate material synthesized by instantaneous Joule heat sintering and preparation method and application thereof
CN115650199A (en) * 2022-11-14 2023-01-31 中碳国际新能源科技(天津)有限公司 Rapid high-temperature thermal shock method for synthesizing phosphoric acid method for preparing vanadium sodium/carbon anode composite material

Similar Documents

Publication Publication Date Title
Chen et al. Preparation and electrochemical performance studies on Cr-doped Li3V2 (PO4) 3 as cathode materials for lithium-ion batteries
CN111180709B (en) Carbon nano tube and metal copper co-doped ferrous oxalate lithium battery composite negative electrode material and preparation method thereof
CN110931781A (en) Preparation method and application of biomass carbon/sodium iron fluorophosphate composite material
CN113526483B (en) Ferro-phosphorus sodalite type cathode material and preparation method and application thereof
CN102104143A (en) Hydrothermal synthesis method of composite material for high-performance power battery
Nanthagopal et al. An encapsulation of nitrogen and sulphur dual-doped carbon over Li [Ni0. 8Co0. 1Mn0. 1] O2 for lithium-ion battery applications
CN113247962B (en) Battery anode material and method for rapidly synthesizing battery anode material
Chang et al. Synthesis and performance of high tap density LiFePO4/C cathode materials doped with copper ions
CN114665058A (en) Preparation method of lithium ion battery anode material lithium iron manganese phosphate
CN101150191A (en) Anode material lanthanum or Ac adulterated LiFePO4 of lithium ion secondary battery and its making method
CN103996852A (en) Preparation method of novel nano lithium vanadium phosphate positive electrode material
Wu et al. Enhancing performances of Co-free Li-rich Mn-based layered cathode materials via interface modification of multiple-functional Mn3O4 shell
CN103928680A (en) Spray drying auxiliary synthesis method for preparing sheet type lithium manganese phosphate/graphene composite material
CN113540410A (en) Preparation method and application of lithium iron phosphate cathode material synthesized by rapid high-temperature thermal shock method
CN110611091A (en) Method for improving electrochemical performance of lithium-rich manganese-based positive electrode material
Ding et al. Modified solid-state reaction synthesized cathode lithium iron phosphate (LiFePO4) from different phosphate sources
Liu et al. The effect of calcination temperature on combustion preparation of ZnFe2O4 as anode for lithium batteries
ZHONG et al. Synthesis of LiMnPO4/C composite material for lithium ion batteries by sol-gel method
Chen et al. Enabling improved electrochemical properties by uniform sodium doping for Li-rich Mn-based Li1. 2Mn0. 54Ni0. 13Co0. 13O2 layered oxide
CN107834054B (en) Preparation method of lithium nickel manganese oxide-graphene composite material for lithium ion battery
Liu et al. Excellent cycling performance of high-nickel single-crystal cathode material by a well-tailored binary molten-salt method
CN114864894A (en) High-pressure-resistant coating-layer-modified lithium-rich manganese-based positive electrode material and preparation method and application thereof
KR102394000B1 (en) Phosphate positive electrode active material for lithium secondary battery and a method of manufacturing the same
Gao et al. Synthesis of LiFePO 4/C as cathode material by a novel optimized hydrothermal method
CN102593447A (en) Metal doping method of lithium iron phosphate anode material

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination