CN104485450A - Preparation method of lithium ion battery anode material FeV2O4 - Google Patents

Preparation method of lithium ion battery anode material FeV2O4 Download PDF

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CN104485450A
CN104485450A CN201410789937.1A CN201410789937A CN104485450A CN 104485450 A CN104485450 A CN 104485450A CN 201410789937 A CN201410789937 A CN 201410789937A CN 104485450 A CN104485450 A CN 104485450A
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lithium ion
ion battery
fev
preparation
battery negative
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CN104485450B (en
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张佳峰
张宝
李晖
袁新波
王小玮
郑俊超
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Central South University
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/523—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron for non-aqueous cells
    • 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
    • H01M4/139—Processes of manufacture
    • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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

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

Abstract

The invention discloses a preparation method of lithium ion battery anode material FeV2O4. The preparation method comprises the following steps: (1) adding ferrous oxalate solution and ammonium metavanadate solution in a stirring reaction kettle simultaneously under a protective atmosphere according to the ratio of 1: 2 of a ferrous ion concentration to a vanadium ion concentration, stirring, reacting, adjusting the pH value to 2-6, and further reacting for 1-4h to obtain a dark blue turbid liquid; (2) adding the turbid liquid obtained in the step (1) in ethyl alcohol with volume equivalent to 1-3% of the volume of the turbid liquid, and then carrying out spray-drying to obtain a precursor material; and (3) carrying out heat treatment on the precursor material obtained in the step (2) for 8-15h at 200-400 DEG C under the protective atmosphere, and then adding liquid nitrogen and quenching to obtain the lithium ion battery anode material FeV2O4. The method disclosed by the invention is low in heat treatment temperature; the prepared FeV2O4 anode material particles are of a microspherical structure, high in tap density, high in charge-discharge characteristics and long in cycle life.

Description

A kind of lithium ion battery negative material FeV 2o 4preparation method
Technical field
The present invention relates to a kind of preparation method of lithium ion battery negative material, be specifically related to a kind of lithium ion battery negative material FeV 2o 4preparation method.
Background technology
At present, in the commercially producing of battery, battery cathode mainly uses graphite manufacture, but no matter is native graphite or Delanium, and its theoretical specific capacity is all only 372mAh/g.Although graphite cathode has cheapness, advantage that fail safe is good, along with the exploitation of some height ratio capacity positive electrodes, the graphite of lower specific capacity can not meet the requirement matched with positive electrode as negative pole.
Novel negative material emerges in an endless stream, as lithium titanate, agraphitic carbon, Si-C composite material, kamash alloy, metal alloy, Graphene etc.Although Novel anode material differs from one another, also do not have any material to have absolute predominance at present, each enterprise, mechanism are are also actively researching and developing various new material.As lithium titanate good cycle, but theoretical capacity only has 175mAh/g, and volume and capacity ratio does not have advantage especially, is difficult to meet electric motor car and hybrid electric vehicle to the requirement of cell high-capacity.Therefore, exploitation have height ratio capacity, high charge-discharge efficiencies, long circulation life Novel cathode material for lithium ion battery pole very urgent.
The stationarity of the specific discharge capacity of electrode, cycle performance and charge and discharge curve because of the kind of material different and there is very big-difference.As Li 3feN 2during as cathode of lithium battery, discharge capacity is that 150mAh/g, discharge potential are at 1.3V(vs Li/Li +) near, charge and discharge curve is very smooth, and discharge off is delayed, but capacity has obvious decay; Li 3-xco xn has the high discharge capacity of 900mAh/g, and discharge potential is at about 1.0V, but charge and discharge curve is not too steady, has the delayed and capacity attenuation of obvious current potential.At present, this kind of material will reach practical application, also needs further further investigation.When some metal is as metal embedding lithiums such as Sn, Si, Al, will be formed containing the very high lithium-metal alloy of lithium amount, the theoretical capacity as Sn is 990mAh/cm 3, close to 10 times of the theoretical volume specific capacity of graphite.But the subject matter of alloy material of cathode is that efficiency is lower and cyclical stability is poor first, must solve the problem that the bulk effect of negative material in repeated charge process causes electrode structure to destroy.And simple metal material negative pole cycle performance is very poor, fail safe is also bad.The Co of the diameter 3 ~ 7 μm that F.F.Tao etc. adopt the self assembly of wet chemical method synthesis of nano sheet to be formed 3o 4tiny balloon, the nano particle that nanometer sheet is about 50nm by diameter forms, and first discharge specific capacity is 1048mAh/g, but just decays to 390mAh/g to second circulation specific discharge capacity.The method of solvent heat and calcining such as L.Liu has synthesized nanometer sheet base NiO microballoon, find that the temperature of reaction, time and surfactant have material impact for product morphology, during 50mA/g constant current charge-discharge, first discharge specific capacity is about 1570mAh/g, but during charging, special capacity fade reaches 500mAh/g, and cyclical stability is poor.
At present, China's vanadium, iron resource are abundant, and raw material sources is extensive, with low cost.Therefore, FeV 2o 4it is a lithium ion battery negative material with very large potentiality and value.Current laboratory prepares FeV by solid-phase ball milling method 2o 4but various aspects of performance is all poor.
Summary of the invention
Technical problem to be solved by this invention is, provides a kind of synthesis temperature low, and condition is easy to control, and synthetic method is simple, and product tap density and electrochemical performance, utilize spraying dry to work in coordination with the lithium ion battery negative material FeV of heat treatment quenching technology 2o 4preparation method.
The technical solution adopted for the present invention to solve the technical problems is: a kind of lithium ion battery negative material FeV 2o 4preparation method, comprise the following steps:
(1) by ferrous oxalate solution and the ammonium metavanadate solution ratio in solution ferrous ions and vanadium ion mol ratio 1:2, under protective atmosphere, join stirring reaction in stirred autoclave simultaneously, after reinforced end, regulate pH value of solution to 2 ~ 6(preferably 4 ~ 5.5), continue reaction 1 ~ 4h(preferably 1.5 ~ 3h), obtain navy blue suspension-turbid liquid;
(2) step (1) gained suspension-turbid liquid is added the ethanol being equivalent to its volume 1 ~ 3%, then carry out spraying dry, obtain presoma material;
(3) by step (2) gained presoma material under protective atmosphere, in 200 ~ 400 DEG C of (preferably 300 ~ 380 DEG C) heat treatment 8 ~ 15h(preferably 9 ~ 12h), then add liquid nitrogen quenching, obtain lithium ion battery negative material FeV 2o 4.
Further, in step (1), described ferrous oxalate solution and ammonium metavanadate solution are 200 ~ 600mL/h(preferably 300 ~ 500mL/h by the speed that solution adds).
Further, in step (2), described spray-dired charging rate is 400 ~ 1200 mL/h(preferably 600 ~ 1000 mL/h), dry inlet temperature is 150 ~ 250 DEG C (preferably 200 ~ 230 DEG C), and leaving air temp is 80 ~ 150 DEG C (preferably 100 ~ 130 DEG C).
Further, in step (1), the speed of described stirring is 200 ~ 400rpm(preferably 250 ~ 350rpm).
Further, in step (1) and (3), described protective atmosphere is one or more in argon gas, nitrogen, hydrogen, carbon dioxide or carbon monoxide.
In step (2), described in the ethanol that adds can play the effect of discrete particles, and spraying dry can play the effect of spheroidizing of particles.
In step (3), after by the heat treatment of presoma material, carry out quenching and material can be made finer and close.
The inventive method utilizes spraying dry to work in coordination with heat treatment quenching technology to prepare ion battery cathode material FeV 2o 4, in the suspension-turbid liquid that synthetic reaction can be made to obtain, Granular composite is more even, and the presoma composition obtained with this is also just more even.Gained lithium ion battery negative material FeV of the present invention 2o 4have microspheroidal structure (average grain diameter about 3 μm), because micro-sphere structure can make material finer and close, so effectively can improve the Physical Processing performance of negative material, improve a lot to the tap density of material especially, tap density is by 1.14g/cm 3bring up to 1.72g/cm 3, make the volume energy density of battery increase by 50%.On the other hand, FeV 2o 4similar with graphite, alloy and metal oxide, the deintercalation site of lithium ion can be provided equally, and there is active chemical property (V due to vanadium 2+to V 5+), therefore, FeV 2o 4there is higher specific capacity (~ 800mAh/g), gained lithium ion battery negative material FeV of the present invention 2o 4under 0.1 ~ 2.5V voltage, 0.1C first discharge specific capacity can reach 866.5mAh/g, and 1C first discharge specific capacity can reach 708.2mAh/g, and 0.1C circulates after 50 times and still keeps 652.6mAh/g.Therefore, gained lithium ion battery negative material FeV of the present invention 2o 4there is excellent chemical property, present good cycle life, effectively solve the shortcoming of metal oxide negative material capacity attenuation.The raw materials used wide material sources of the present invention, technological process is simple, and react temperature required low, particle has microspheroidal structure, and tap density is high, and has higher charge-discharge characteristic and good cycle life.
Accompanying drawing explanation
Fig. 1 is the XRD figure of the embodiment of the present invention 1 sample;
Fig. 2 is the SEM diffraction pattern of the embodiment of the present invention 1 sample;
Fig. 3 is 0.1C, 1C discharge curve first of the embodiment of the present invention 1 sample;
Fig. 4 is the discharge cycles figure under the 0.1C multiplying power of the embodiment of the present invention 1 sample;
Fig. 5 is 0.1C, 1C discharge curve first of comparative example 1 sample of the present invention;
Fig. 6 is the discharge cycles figure under the 0.1C multiplying power of comparative example 1 sample of the present invention.
Embodiment
Below in conjunction with embodiment and accompanying drawing, the invention will be further described.
embodiment 1
(1) 0.01mol ferrous oxalate is dissolved in the deionized water of 100mL and is made into the solution that concentration is 0.1mol/L; 0.02mol ammonium metavanadate is dissolved in the deionized water of 100mL and is made into the solution that concentration is 0.2mol/L; Then the ferrous oxalate solution prepared and ammonium metavanadate solution are all joined in stirred autoclave with the speed of 400mL/h under high pure nitrogen (concentration>=99.99%) atmosphere simultaneously, control mixing speed is 300rpm, pH to 5 is regulated with ammoniacal liquor after reinforced end, continue reaction 2h, obtain navy blue suspension-turbid liquid; (2) by adding the ethanol of 4mL in step (1) gained suspension-turbid liquid, then carry out spraying dry, charging rate is 800 mL/h, and dry inlet temperature is 220 DEG C, and leaving air temp is 120 DEG C, obtains presoma material; (3) by step (2) gained presoma material under the protection of high pure nitrogen (concentration>=99.99%) in 350 DEG C of heat treatment 10h, then add 2mL liquid nitrogen and carry out quenching, obtain lithium ion battery negative material FeV 2o 4, tap density is 1.72g/cm 3.
As shown in Figure 1, FeV 2o 4crystalline structure be tending towards amorphous state, there is no complete crystal structure; As shown in Figure 2, FeV 2o 4pattern be spherical, the density of product is high.
The assembling of battery: take the FeV obtained by 0.4g 2o 4, add 0.05g acetylene black and make conductive agent and 0.05g NMP(N-methyl pyrrolidone) and make binding agent, be coated in after mixing on Copper Foil and make negative plate, take metal lithium sheet as positive pole in vacuum glove box, with Celgard 2300 for barrier film, 1mol/L LiPF 6/ EC:DMC(volume ratio 1:1) be electrolyte, be assembled into the button cell of CR2025,0.1C first discharge specific capacity is that 866.5mAh/g(is see Fig. 3), after 50 circulations, specific discharge capacity still reaches 652.6mAh/g(see Fig. 4); 1C first discharge specific capacity is that 708.2 mAh/g(are see Fig. 3).
embodiment 2
(1) 0.01mol ferrous oxalate is dissolved in the deionized water of 100mL and is made into the solution that concentration is 0.1mol/L; 0.02mol ammonium metavanadate is dissolved in the deionized water of 100mL and is made into the solution that concentration is 0.2mol/L; Then the ferrous oxalate solution prepared and ammonium metavanadate solution are all joined in stirred autoclave with the speed of 200mL/h under high-purity argon gas (concentration>=99.99%) atmosphere simultaneously, control mixing speed is 200rpm, pH to 2 is regulated with ammoniacal liquor after reinforced end, continue reaction 1h, obtain navy blue suspension-turbid liquid; (2) by adding the ethanol of 2mL in step (1) gained suspension-turbid liquid, then carry out spraying dry, charging rate is 400 mL/h, and dry inlet temperature is 150 DEG C, and leaving air temp is 80 DEG C, obtains presoma material; (3) by step (2) gained presoma material under the protection of high-purity argon gas (concentration>=99.99%) in 200 DEG C of heat treatment 8h, then add 1mL liquid nitrogen and carry out quenching, obtain lithium ion battery negative material FeV 2o 4, tap density is 1.58g/cm 3.
The assembling of battery: take the FeV obtained by 0.4g 2o 4, add 0.05g acetylene black and make conductive agent and 0.05g NMP(N-methyl pyrrolidone) and make binding agent, be coated in after mixing on Copper Foil and make negative plate, take metal lithium sheet as positive pole in vacuum glove box, with Celgard 2300 for barrier film, 1mol/L LiPF 6/ EC:DMC(volume ratio 1:1) be electrolyte, be assembled into the button cell of CR2025,0.1C first discharge specific capacity is 786.5mAh/g, and after 50 circulations, specific discharge capacity is 601.8mAh/g; 1C first discharge specific capacity is 650.2 mAh/g.
embodiment 3
(1) 0.01mol ferrous oxalate is dissolved in the deionized water of 100mL and is made into the solution that concentration is 0.1mol/L; 0.02mol ammonium metavanadate is dissolved in the deionized water of 100mL and is made into the solution that concentration is 0.2mol/L; Then the ferrous oxalate solution prepared and ammonium metavanadate solution are all joined in stirred autoclave with the speed of 600mL/h under high-purity argon gas (concentration>=99.99%) atmosphere simultaneously, control mixing speed is 400rpm, pH to 6 is regulated with ammoniacal liquor after reinforced end, continue reaction 4h, obtain navy blue suspension-turbid liquid; (2) by adding the ethanol of 6mL in step (1) gained suspension-turbid liquid, then carry out spraying dry, charging rate is 1200 mL/h, and dry inlet temperature is 250 DEG C, and leaving air temp is 150 DEG C, obtains presoma material; (3) by step (2) gained presoma material under the protection of high-purity argon gas (concentration>=99.99%) in 400 DEG C of heat treatment 15h, then add 5mL liquid nitrogen and carry out quenching, obtain lithium ion battery negative material FeV 2o 4, tap density is 1.62g/cm 3.
The assembling of battery: take the FeV obtained by 0.4g 2o 4, add 0.05g acetylene black and make conductive agent and 0.05g NMP(N-methyl pyrrolidone) and make binding agent, be coated in after mixing on Copper Foil and make negative plate, take metal lithium sheet as positive pole in vacuum glove box, with Celgard 2300 for barrier film, 1mol/L LiPF 6/ EC:DMC(volume ratio 1:1) be electrolyte, be assembled into the button cell of CR2025,0.1C first discharge specific capacity is 796.5mAh/g, and after 50 circulations, specific discharge capacity is 611.7mAh/g; 1C first discharge specific capacity is 685.2 mAh/g.
comparative example 1
(1) 0.01mol ferrous oxalate and 0.02mol ammonium metavanadate are directly carried out ball milling under high pure nitrogen (concentration>=99.99%) atmosphere, control ball milling speed is 300r/min, and Ball-milling Time is 2h, obtains presoma material; (2) by step (1) gained presoma material under the protection of high pure nitrogen (concentration>=99.99%) in 350 DEG C of heat treatment 10h, then add 2mL liquid nitrogen, obtain lithium ion battery negative material FeV 2o 4, tap density is 1.14g/cm 3.
The assembling of battery: take the FeV obtained by 0.4g 2o 4, add 0.05g acetylene black and make conductive agent and 0.05g NMP(N-methyl pyrrolidone) and make binding agent, be coated in after mixing on Copper Foil and make negative plate, take metal lithium sheet as positive pole in vacuum glove box, with Celgard 2300 for barrier film, 1mol/L LiPF 6/ EC:DMC(volume ratio 1:1) be electrolyte, be assembled into the button cell of CR2025,0.1C first discharge specific capacity is that 778.9mAh/g(is see Fig. 5), after 50 circulations, specific discharge capacity is that 226.4mAh/g(is see Fig. 6); 1C first discharge specific capacity is that 557.2 mAh/g(are see Fig. 5).
Compared with example 1, the tap density of product is obviously on the low side, and chemical property is obviously poor, and especially cyclical stability is poor.

Claims (10)

1. a lithium ion battery negative material FeV 2o 4preparation method, it is characterized in that: comprise the following steps:
(1) by ferrous oxalate solution and the ammonium metavanadate solution ratio in solution ferrous ions and vanadium ion mol ratio 1:2, under protective atmosphere, join stirring reaction in stirred autoclave simultaneously, after reinforced end, regulate pH value of solution to 2 ~ 6, continue reaction 1 ~ 4h, obtain navy blue suspension-turbid liquid;
(2) step (1) gained suspension-turbid liquid is added the ethanol being equivalent to its volume 1 ~ 3%, then carry out spraying dry, obtain presoma material;
(3) by step (2) gained presoma material under protective atmosphere, in 200 ~ 400 DEG C of heat treatment 8 ~ 15h, then add liquid nitrogen quenching, obtain lithium ion battery negative material FeV 2o 4.
2. lithium ion battery negative material FeV according to claim 1 2o 4preparation method, it is characterized in that: in step (1), the speed that described ferrous oxalate solution and ammonium metavanadate solution add by solution is 200 ~ 600mL/h.
3. lithium ion battery negative material FeV according to claim 1 or 2 2o 4preparation method, it is characterized in that: in step (2), described spray-dired charging rate is 400 ~ 1200 mL/h, and dry inlet temperature is 150 ~ 250 DEG C, and leaving air temp is 80 ~ 150 DEG C.
4. lithium ion battery negative material FeV according to claim 1 or 2 2o 4preparation method, it is characterized in that: in step (1), the speed of described stirring is 200 ~ 400rpm.
5. lithium ion battery negative material FeV according to claim 1 or 2 2o 4preparation method, it is characterized in that: in step (1) and (3), described protective atmosphere is one or more in argon gas, nitrogen, hydrogen, carbon dioxide or carbon monoxide.
6. lithium ion battery negative material FeV according to claim 1 or 2 2o 4preparation method, it is characterized in that: in step (1), regulate pH value of solution to 4 ~ 5.5, continue reaction time be 1.5 ~ 3h.
7. lithium ion battery negative material FeV according to claim 1 or 2 2o 4preparation method, it is characterized in that: in step (3), described heat treated temperature is 300 ~ 380 DEG C, and the time is 9 ~ 12h.
8. lithium ion battery negative material FeV according to claim 2 2o 4preparation method, it is characterized in that: in step (1), the speed that described ferrous oxalate solution and ammonium metavanadate solution add by solution is 300 ~ 500mL/h.
9. lithium ion battery negative material FeV according to claim 3 2o 4preparation method, it is characterized in that: in step (2), described spray-dired charging rate is 600 ~ 1000 mL/h, and dry inlet temperature is 200 ~ 230 DEG C, and leaving air temp is 100 ~ 130 DEG C.
10. lithium ion battery negative material FeV according to claim 4 2o 4preparation method, it is characterized in that: in step (1), the speed of described stirring is 250 ~ 350rpm.
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106311213A (en) * 2016-08-30 2017-01-11 河南康宁特环保科技股份有限公司 Sulfur-resistant and water-resistant low-temperature denitration catalyst and preparation method thereof
CN108346796A (en) * 2017-01-23 2018-07-31 中原大学 Sodium rechargeable battery
CN111204811A (en) * 2020-01-13 2020-05-29 中国科学技术大学 Preparation method of vanadium-based spinel material and preparation method of battery anode
CN113135599A (en) * 2021-05-19 2021-07-20 攀钢集团攀枝花钢铁研究院有限公司 Preparation method of vanadium iron spinel

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003252814A (en) * 2002-02-28 2003-09-10 Nippon Shokubai Co Ltd Method for producing nucleus-methylated aromatic compound and method for producing ortho-methylphenol compounds
CN101428781A (en) * 2008-12-08 2009-05-13 广州丰江电池新技术有限公司 Conglobation type nanostructured lithium iron phosphate anode material and method for producing the same
CN102361080A (en) * 2011-10-31 2012-02-22 中南大学 Method for preparing lithium iron phosphate-lithium vanadium phosphate by quenching method
CN103825025A (en) * 2014-02-27 2014-05-28 三峡大学 Negative electrode material FeVO4 of lithium ion battery and preparation method thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003252814A (en) * 2002-02-28 2003-09-10 Nippon Shokubai Co Ltd Method for producing nucleus-methylated aromatic compound and method for producing ortho-methylphenol compounds
CN101428781A (en) * 2008-12-08 2009-05-13 广州丰江电池新技术有限公司 Conglobation type nanostructured lithium iron phosphate anode material and method for producing the same
CN102361080A (en) * 2011-10-31 2012-02-22 中南大学 Method for preparing lithium iron phosphate-lithium vanadium phosphate by quenching method
CN103825025A (en) * 2014-02-27 2014-05-28 三峡大学 Negative electrode material FeVO4 of lithium ion battery and preparation method thereof

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106311213A (en) * 2016-08-30 2017-01-11 河南康宁特环保科技股份有限公司 Sulfur-resistant and water-resistant low-temperature denitration catalyst and preparation method thereof
CN108346796A (en) * 2017-01-23 2018-07-31 中原大学 Sodium rechargeable battery
CN111204811A (en) * 2020-01-13 2020-05-29 中国科学技术大学 Preparation method of vanadium-based spinel material and preparation method of battery anode
CN111204811B (en) * 2020-01-13 2021-05-07 中国科学技术大学 Preparation method of vanadium-based spinel material and preparation method of battery anode
CN113135599A (en) * 2021-05-19 2021-07-20 攀钢集团攀枝花钢铁研究院有限公司 Preparation method of vanadium iron spinel
CN113135599B (en) * 2021-05-19 2022-07-29 攀钢集团攀枝花钢铁研究院有限公司 Preparation method of vanadium iron spinel

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