CN101577328B - Preparation method of LiFePO4/C composite cathode material - Google Patents

Preparation method of LiFePO4/C composite cathode material Download PDF

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CN101577328B
CN101577328B CN200910084343XA CN200910084343A CN101577328B CN 101577328 B CN101577328 B CN 101577328B CN 200910084343X A CN200910084343X A CN 200910084343XA CN 200910084343 A CN200910084343 A CN 200910084343A CN 101577328 B CN101577328 B CN 101577328B
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杨文胜
魏珣
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Beijing University of Chemical Technology
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Abstract

The invention relates to a preparation method of a LiFePO4/C composite cathode material, belonging to the technical field of the cathode material of a lithium ion battery. The invention uses differentactions of an inorganic carbon source material and an organic carbon source material, respectively adds two types of carbon source materials in different stages of the reaction process and synthesizes the LiFePO4/C composite cathode material with sphere-like shape, uniform particle size distribution and good electrochemical property. The preparation method has the advantages of simple technique,low material cost and the like and is suitable for large-scale production.

Description

A kind of LiFePO 4The preparation method of/C composite positive pole
Technical field
The invention belongs to the anode material for lithium-ion batteries preparing technical field, particularly relate to a kind of LiFePO 4The preparation method of/C composite positive pole.
Background technology
LiFePO 4Be the orthorhombic system olivine structural, belong to the Pnmb space group.LiFePO 4Theoretical specific capacity be 170mAh/g, when the electrochemistry removal lithium embedded distortion of lattice little, Stability Analysis of Structures has extended cycle life, and is safe, cheap, is a kind of comparatively ideal large-scale anode material for lithium-ion batteries.But LiFePO 4Electronic conductivity and ionic diffusion coefficient low, cause its capacity attenuation when heavy-current discharge very fast, high rate performance is poor, has limited LiFePO 4Practical application.
Utilize material with carbon element to prepare LiFePO 4/ C composite positive pole is to LiFePO 4The effective means of modification, wherein the effect of carbon mainly shows as: the electron conduction of (1) reinforced composite; (2) stop LiFePO in the roasting process 4Grain growth reduces the lithium ion the evolving path; (3)+3 valency iron materials are reduced to+divalent, or in the assurance course of reaction+divalent iron is not oxidized to high valence state.
As preparation LiFePO 4The carbon source material of/C composite positive pole mainly comprises with conductive black, graphite, acetylene black etc. being the DIC source material of representative and being the organic carbon source material of representative with sucrose, glucose, organic polymer etc.The DIC source material has good reproducibility ,+3 valency iron materials can be reduced to+divalent, or in the assurance course of reaction+divalent iron is not oxidized to high valence state; The DIC source material has satisfactory electrical conductivity, can strengthen LiFePO 4The intercrystalline electrical conductivity.The organic carbon source material also has reproducibility after carbonization, but reduction reaction temperature is higher; In the organic carbon source material carbonisation, at melting process of 300～400 ℃ of experience, therefore can be at LiFePO 4The surface forms even coating layer, the LiFePO that helps forming stable conductive network in composite material and form specific morphology 4Aggregate.
Reporting in the document, adopting a kind of carbon source material to prepare LiFePO more 4/ C combination electrode material utilizes two kinds of dissimilar carbon source materials to prepare LiFePO simultaneously 4The report of/C composite material is less.
At document (1) Solid State Ionics, in 2008,179,1736～1739, people such as Chunyan Lai adopt two kinds of different carbon source materials of carbon gel and glucose to prepare LiFePO 4/ C combination electrode material.Concrete processing step is: with ferrous oxalate, ammonium dihydrogen phosphate, lithium hydroxide, carbon gel is raw material; mixed 5 hours for the dispersant ball milling with ethanol; with the ball milling mixed material under nitrogen protection in 300 ℃ of roastings 10 hours; then with glucose mixing and ball milling 2 hours; again with the ball milling mixed material under nitrogen protection in 750 ℃ of roastings 24 hours, obtain LiFePO 4/ C composite material.It is raw material that the method adopts ferrous oxalate, and iron exists with+divalent form, and the carbon gel mainly plays the effect that strengthens conductivity, and its reduction is embodied; In addition, the ferrous oxalate price is higher, and severe reaction conditions, so this method production cost is higher.
At document (2) Chinese invention patent, among the publication number CN 101152961A, Wang Ruying etc. also adopt two kinds of different carbon source materials to prepare LiFePO 4/ C composite material.Concrete processing step is: with lithium dihydrogen phosphate, and di-iron trioxide, DIC source material (acetylene black or crystalline flake graphite) and doping element compound mix, and are that the dispersant ball milling is even with water; The slurry that ball milling is mixed carries out spray drying, obtains the spherical solid phase powder of class of homogeneous grain diameter; In this solid phase powder, drop into organic carbon source material (sucrose or glucose), mix by dry ball milling, then with the powder body material that mixes under the nitrogen atmosphere protection 300～400 ℃ carry out the roasting first time, temperature retention time is 4～48 hours; With the product ball mill crushing behind the bakes to burn the article 4～48 hours, 200 orders sieved then; Product after sieving carries out after baking in 600～800 ℃ under nitrogen atmosphere protection, temperature retention time is 4～48 hours, after the stove cooling, obtains LiFePO 4/ C composite material.This inventive method 300～400 ℃ carry out the roasting first time after, organic carbon source material (sucrose or glucose) fusion and at LiFePO 4The surface forms coating layer, but the ball mill crushing process of carrying out subsequently makes coating layer destroy again, so the effect of organic carbon source material is brought into play.
Summary of the invention
The object of the present invention is to provide a kind of LiFePO 4The preparation method of/C composite positive pole, utilize the not same-action of DIC source material and organic carbon source material, two kinds of carbon source materials are added respectively in the different phase of course of reaction, with the synthetic LiFePO that has the spherical looks of class, particle size distribution homogeneous and have the good electrical chemical property 4/ C composite positive pole.
Concrete processing step of the present invention is as follows:
A. according to Li: Fe: C is that 1: 1: 1 molar ratio takes by weighing LiH respectively 2PO 4, Fe 2O 3, (conductive black, particle diameter are 10～20nm) and mix the DIC source material; Consumption according to 1～4 times of this solid mixture gross mass adds absolute ethyl alcohol, and obtains slurry in 8～24 hours with 250～400 rev/mins rotating speed ball milling; Slurry was dried 12～24 hours in 60～80 ℃ of baking ovens.
B. the product after will drying was warming up to 300～450 ℃ and constant temperature 2～6 hours with 3～10 ℃/minute speed under nitrogen atmosphere, be cooled to room temperature with stove then, obtained the preroast product.
C. accounting for preroast product quality mark according to organic carbon source material (sucrose) is that 3.9～21.5% ratio takes by weighing organic carbon source material and preroast product respectively and mixes; Consumption according to 1～4 times of preroast product gross mass adds absolute ethyl alcohol, and obtains slurry in 8～24 hours with 250～400 rev/mins rotating speed ball milling; Slurry was dried 12～24 hours in 60～80 ℃ of baking ovens.
D. the product after will drying was warming up to 600～700 ℃ and constant temperature 4～10 hours with 3～10 ℃/minute speed under nitrogen atmosphere, be cooled to room temperature with stove then, obtained LiFePO 4/ C composite material.
Adopt the U.S. Perkin Elmer Diamond of PE company type heat analysis-GC-MS that sample is carried out hot analytical test.Take by weighing 20.788g LiH 2PO 4, 15.969g Fe 2O 3With 3.4g DIC source material conductive black and mixing, add the 100mL absolute ethyl alcohol, mixed 12 hours with 350 rev/mins rotating speed ball millings, then the product behind the ball milling was dried 12 hours in 65 ℃ of baking ovens, carry out heat analysis, the result is as depicted in figs. 1 and 2.CO among weightlessness among Fig. 1 in 610～740 ℃ of scopes and Fig. 2 in this temperature range 2The peak reduces Fe corresponding to conductive black 2O 3Reaction.Take by weighing 20.788g LiH 2PO 4, 15.969g Fe 2O 3With 14g organic carbon source material sucrose and mixing, add the 100mL absolute ethyl alcohol, mixed 12 hours with 350 rev/mins rotating speed ball millings, then the product behind the ball milling was dried 12 hours in 65 ℃ of baking ovens, carry out heat analysis, the result is as shown in Figure 3 and Figure 4.In conjunction with the result of study of document Electrochimica Acta54 (2009) 2861-2868, the CO among the weightlessness among Fig. 3 before 747 ℃ and Fig. 4 before 747 ℃ 2The peak is corresponding to the carbonisation of sucrose, the CO among the weightlessness among Fig. 3 in 747～923 ℃ of scopes and Fig. 4 in this temperature range 2The peak is corresponding to the sucrose reduction Fe of carbonization 2O 3Reaction.Hence one can see that, DIC source material reduction Fe 2O 3Temperature be lower than organic carbon source material reduction Fe 2O 3Temperature.
Adopt day island proper Tianjin 6000 type X-ray diffractometers to characterize the product crystal structure.The test result (see figure 5) shows the LiFePO that adopts the inventive method can prepare olivine structural 4, and crystal carbon impurity diffraction maximum does not appear, and illustrate that the carbon in the product of the present invention exists with unformed form, therefore can not influence its chemical property owing to the existence of crystal carbon.
Adopt the S4700 of HIT type field emission scanning electron microscope to characterize the microscopic appearance of product.The test result (see figure 6) shows the LiFePO that adopts the inventive method preparation 4/ C composite material has the spherical looks of class, and average grain diameter is 1 μ m.
Adopt Mastersizer 2000 laser particle size analyzers of Britain Ma Erwen company that the granularity of product is carried out analysis and characterization.The test result (see figure 7) shows that adopting the inventive method can prepare average grain diameter is 1 μ m, and the LiFePO of particle size distribution homogeneous 4/ C composite material.Adopt different throwing carbon modes and single DIC source material (seeing Comparative Examples 1 and Comparative Examples 2), the particle size range wider distribution of prepared sample (seeing Fig. 8 and Fig. 9).
With LiFePO 4/ C composite positive pole and commercially available acetylene black conductive agent and Kynoar (PVDF) binding agent by 80: 10: 10 quality than mixed pressuring plate, in 120 ℃ of vacuum (＜10Pa) dry 24 hours.As negative pole, adopt Celgard 2400 barrier films, the LiPF of 1mol/L with metal lithium sheet 6+ EC+DMC (EC/DMC volume ratio 1: 1) is an electrolyte, at the German M. Braun Unlab of company type dry argon gas glove box (H 2Be assembled into Experimental cell among the O＜1ppm, O2＜1ppm), adopt the blue electric CT2001A type cell tester in Wuhan to carry out electrochemical property test.Test result such as Figure 10 are shown in 11 and 12.With the LiFePO that adopts different throwing carbon modes and single DIC source material (seeing Comparative Examples 1 and Comparative Examples 2) to make 4/ C compares, the LiFePO of the inventive method preparation 4The electrochemistry cyclical stability of/C composite positive pole obviously is better than comparative example, and has shown good high rate performance.
Characteristics of the present invention and advantage are: the present invention utilizes the not same-action of two kinds of carbon source materials in course of reaction, i.e. the LiFePO with the spherical looks of class and particle size distribution homogeneous is prepared in the coating effect of the reduction of DIC source material and organic carbon source material 4/ C composite positive pole, and have excellent electrochemical properties.Advantages such as it is simple that preparation method provided by the invention has technology, and cost of material is low, suitability for scale production.
Description of drawings:
Fig. 1. contain the thermogravimetric curve of DIC source material sample.Abscissa is a temperature, unit be degree centigrade (℃); Ordinate is a weight-loss ratio, and unit is percentage (%).
Fig. 2. contain DIC source material decomposed sample product C O 2The mass spectral analysis curve.Abscissa is a temperature, unit be degree centigrade (℃); Ordinate is an ionic strength, and unit is absolute unit (a.u.).
Fig. 3. contain the thermogravimetric curve of organic carbon source material sample.Abscissa is a temperature, unit be degree centigrade (℃); Ordinate is a weight-loss ratio, and unit is percentage (%).
Fig. 4. contain organic carbon source material decomposed sample product C O 2The mass spectral analysis curve.Abscissa is a temperature, unit be degree centigrade (℃); Ordinate is an ionic strength, and unit is absolute unit (a.u.).
Fig. 5. embodiment 1 preparation LiFePO 4The XRD spectra of/C composite material.Abscissa is angle 2 θ, unit for the degree (°); Ordinate is a diffracted intensity, and unit is absolute unit (a.u.).
Fig. 6. embodiment 1 preparation LiFePO 4The stereoscan photograph of/C composite material.
Fig. 7. embodiment 1 preparation LiFePO 4The grading curve of/C composite material.Abscissa is a granularity, and unit is a micron (μ m); Ordinate is a percentage by volume, and unit is percentage (%).
Fig. 8. Comparative Examples 1 preparation LiFePO 4The grading curve of/C composite material.Abscissa is a granularity, and unit is a micron (μ m); Ordinate is a percentage by volume, and unit is percentage (%).
Fig. 9. Comparative Examples 2 preparation LiFePO 4The grading curve of/C composite material.Abscissa is a granularity, and unit is a micron (μ m); Ordinate is a percentage by volume, and unit is percentage (%).
Figure 10. the LiFePO that different throwing carbon modes prepare 4The electrochemistry cycle performance curve of/C composite material.Abscissa is a cycle period, and unit is week; Ordinate is a specific discharge capacity, and unit is MAH/gram (mAh/g).Curve a-embodiment 1 preparation LiFePO 4The electrochemistry cycle performance curve of/C composite material; Curve b-Comparative Examples 1 preparation LiFePO 4The electrochemistry cycle performance curve of/C composite material; Curve c-Comparative Examples 2 preparation LiFePO 4The electrochemistry cycle performance curve of/C composite material.
Figure 11. embodiment 1 preparation LiFePO 4The high rate performance curve of/C composite material.Abscissa is a cycle period, and unit is week; Ordinate is a specific discharge capacity, and unit is MAH/gram (mAh/g).
Figure 12. embodiment 1 preparation LiFePO 4The first charge-discharge curve of/C composite material.Abscissa specific discharge capacity, unit are MAH/gram (mAh/g); Ordinate is a voltage, and unit is a volt (V).
Embodiment 1
Take by weighing 20.788g LiH 2PO 4, 15.969g Fe 2O 3, the 2.4g conductive black also mixes, and then mixed material is joined in the 100mL absolute ethyl alcohol, mixes 12 hours with 350 rev/mins rotating speed ball millings, and the product behind the ball milling was dried 12 hours in 65 ℃.Take by weighing the sample after the 20g oven dry, under nitrogen atmosphere, be warming up to 350 ℃ and constant temperature 4 hours, be cooled to room temperature with stove then with 5 °/minute speed.Add 4.25g sucrose in the preroast product, add the 70mL absolute ethyl alcohol as dispersant, with 350 rev/mins rotating speed ball millings 12 hours, the product behind the ball milling was in 65 ℃ of oven dry 12 hours.Sample after the oven dry under nitrogen atmosphere, is warming up to 650 ℃ and constant temperature 6 hours with 5 °/minute speed, promptly obtains LiFePO after being cooled to room temperature with stove 4/ C composite positive pole.
The XRD test result of this composite positive pole as shown in Figure 5, product is the LiFePO of olivine structural 4About 26.3 °, do not occur crystal carbon impurity diffraction maximum in the XRD figure, illustrate that the carbon in this product exists with unformed form, can not influence its chemical property owing to the existence of crystal carbon.
The stereoscan photograph of this sample as shown in Figure 6, product is the near-spherical particle, particle diameter is about 1 μ m.The laser particle size analysis result as shown in Figure 7, the product average grain diameter is 1 μ m, and the particle size distribution homogeneous.
The electrochemistry cycle performance of this sample is shown in the curve a among Figure 10.This sample has high specific discharge capacity and good electrochemistry cyclical stability.
Figure 11 be embodiment 1 sample at 0.1C, 1C, 2C, 3C, the electrochemistry cycle performance curve under the 5C multiplying power.0.1C average specific discharge capacity is 168mAh/g under the multiplying power, average specific discharge capacity is 146mAh/g under the 1C multiplying power, average specific discharge capacity is 134mAh/g under the 2C multiplying power, and average specific discharge capacity is 124mAh/g under the 3C multiplying power, and average specific discharge capacity is 92mAh/g under the 5C multiplying power.
Figure 12 is the first charge-discharge curve of embodiment 1 sample, and this material has 3.4V charge and discharge platform stably.
Embodiment 2
Take by weighing 20.788g LiH 2PO 4, 15.969g Fe 2O 3, the 2.4g conductive black also mixes, and then mixed material is joined in the 100mL absolute ethyl alcohol, mixes 24 o'clock with 400 rev/mins rotating speed ball millings, and the product behind the ball milling was dried 24 hours in 70 ℃.Take by weighing the sample after the 20g oven dry, under nitrogen atmosphere, be warming up to 450 ℃ and constant temperature 6 hours, be cooled to room temperature with stove then with 10 °/minute speed.Add 4.25g sucrose in the preroast product, add the 70mL absolute ethyl alcohol as dispersant, with 400 rev/mins rotating speed ball millings 24 hours, the product behind the ball milling was in 70 ℃ of oven dry 24 hours.Sample after the oven dry under nitrogen atmosphere, is warming up to 600 ℃ and constant temperature 10 hours with 10 °/minute speed, promptly obtains LiFePO after being cooled to room temperature with stove 4/ C composite positive pole.
The initial charge specific capacity of this sample is 144.22mAh/g, and specific discharge capacity is 130.86mAh/g, and irreversible specific capacity is 13.36mAh/g.First charge-discharge efficiency is 90.8%.And specific discharge capacity becomes the trend that rises gradually, is up to 141.5mAh/g.Circulate after 52 weeks, specific discharge capacity is 141mAh/g, and capability retention is 99.6%.
Embodiment 3
Take by weighing 20.788g LiH 2PO 4, 15.969g Fe 2O 3, the 2.4g conductive black also mixes, and then mixed material is joined in the 100mL absolute ethyl alcohol, mixes 12 hours with 350 rev/mins rotating speed ball millings, and the product behind the ball milling was dried 20 hours in 80 ℃.Take by weighing the sample after the 20g oven dry, under nitrogen atmosphere, be warming up to 350 ℃ and constant temperature 4 hours, be cooled to room temperature with stove then with 3 °/minute speed.Add 4.25g sucrose in the preroast product, add the 70mL absolute ethyl alcohol as dispersant, with 350 rev/mins rotating speed ball millings 12 hours, the product behind the ball milling was in 80 ℃ of oven dry 20 hours.Sample after the oven dry under nitrogen atmosphere, is warming up to 700 ℃ and constant temperature 6 hours with 3 °/minute speed, promptly obtains LiFePO after being cooled to room temperature with stove 4/ C composite positive pole.
This sample initial charge specific capacity is 150.78mAh/g, and specific discharge capacity is 132.67mAh/g, and irreversible specific capacity is 18.11mAh/g.First charge-discharge efficiency is 88%.And specific discharge capacity becomes the trend that rises gradually, is up to 143.76mAh/g.Circulate after 52 weeks, specific discharge capacity is 142.63mAh/g, and capability retention is 99.21%.
Embodiment 4
Take by weighing 20.788g LiH 2PO 4, 15.969g Fe 2O 3, the 2.4g conductive black also mixes, and then mixed material is joined in the 50mL absolute ethyl alcohol, mixes 8 hours with 250 rev/mins rotating speed ball millings, and the product behind the ball milling was dried 12 hours in 60 ℃.Take by weighing the sample after the 20g oven dry, under nitrogen atmosphere, be warming up to 300 ℃ and constant temperature 4 hours, be cooled to room temperature with stove then with 3 °/minute speed.Add 3.328g sucrose in the preroast product, add the 25mL absolute ethyl alcohol as dispersant, with 250 rev/mins rotating speed ball millings 8 hours, the product behind the ball milling was in 60 ℃ of oven dry 12 hours.Sample after the oven dry under nitrogen atmosphere, is warming up to 650 ℃ and constant temperature 4 hours with 3 °/minute speed, promptly obtains LiFePO after being cooled to room temperature with stove 4/ C composite positive pole.
This sample initial charge specific capacity is 146.63mAh/g, and specific discharge capacity is 132.71mAh/g, and irreversible specific capacity is 13.92mAh/g.First charge-discharge efficiency is 90.5%.And specific discharge capacity becomes the trend that rises gradually, is up to 146mAh/g.Circulate after 52 weeks, specific discharge capacity is 145.5mAh/g, and capability retention is 99.6%.
Comparative Examples 1
Take by weighing 20.788g LiH 2PO 4, 15.969g Fe 2O 3, 2.4g conductive black and 8.32g sucrose also mix, and then mixture are joined in the 100mL absolute ethyl alcohol, mix 12 hours with 350 rev/mins rotating speed ball millings, and the product behind the ball milling was dried 12 hours in 65 ℃ of baking ovens.Take by weighing the sample after the 20g oven dry, under nitrogen atmosphere, be warming up to 350 ℃ and constant temperature 4 hours, be warming up to 650 ℃ and constant temperature 6 hours with same speed then, promptly obtained LiFePO after being cooled to room temperature with stove with 5 °/minute speed 4/ C composite positive pole.
The laser particle size analysis result of this sample as shown in Figure 8, the electrochemistry cycle performance is shown in the curve b among Figure 10.
Comparative Examples 2
Take by weighing 20.788g LiH 2PO 4, 15.969g Fe 2O 3, the 3.4g conductive black also mixes, and then mixture is joined in the 100mL absolute ethyl alcohol, mixes 12 hours with 350 rev/mins rotating speed ball millings, and the product behind the ball milling was dried 12 hours in 65 ℃ of baking ovens.Take by weighing the sample after the 20g oven dry, under nitrogen atmosphere, be warming up to 350 ℃ and constant temperature 4 hours, be warming up to 650 ℃ and constant temperature 6 hours with same speed then, promptly obtained LiFePO after being cooled to room temperature with stove with 5 °/minute speed 4/ C composite positive pole.
The laser particle size analysis result of this sample as shown in Figure 9, the electrochemistry cycle performance is shown in the curve c among Figure 10.

Claims (2)

1. LiFePO 4The preparation method of/C composite positive pole, it is characterized in that: two kinds of different carbon source materials are added respectively in the different phase of course of reaction, have the spherical looks of class, particle size distribution homogeneous and LiFePO to bring into play the not same-action of two kinds of carbon source materials, to synthesize with good electrical chemical property 4/ C composite positive pole, concrete processing step is as follows:
A. according to Li: Fe: C is that 1: 1: 1 molar ratio takes by weighing LiH respectively 2PO 4, Fe 2O 3, the DIC source material also mixes; Consumption according to 1～4 times of this solid mixture gross mass adds absolute ethyl alcohol, obtains slurry in 8～24 hours with 250～400 rev/mins rotating speed ball millings; Slurry was dried 12～24 hours in 60～80 ℃ of baking ovens;
B. the sample after will drying was warming up to 300～450 ℃ and constant temperature 2～6 hours with 3～10 ℃/minute speed under nitrogen atmosphere, be cooled to room temperature with stove then, obtained the preroast product;
C. accounting for preroast product quality mark according to the organic carbon source material is that 3.9～21.5% ratio takes by weighing organic carbon source material and preroast product respectively and mixes; Consumption according to 1～4 times of preroast product gross mass adds absolute ethyl alcohol, and obtains slurry in 8～24 hours with 250～400 rev/mins rotating speed ball milling; Slurry was dried 12～24 hours in 60～80 ℃ of baking ovens;
D. the product after will drying was warming up to 600～700 ℃ and constant temperature 4～10 hours with 3～10 ℃/minute speed under nitrogen atmosphere, be cooled to room temperature with stove then, obtained LiFePO 4/ C composite material.
2. according to the described LiFePO of claim 1 4The preparation method of/C composite positive pole is characterized in that: the source material of DIC described in the steps A is a conductive black, and particle diameter is 10～20nm; The material of organic carbon source described in the step C is a sucrose.
CN200910084343XA 2009-05-21 2009-05-21 Preparation method of LiFePO4/C composite cathode material Expired - Fee Related CN101577328B (en)

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CN102544448A (en) * 2010-12-30 2012-07-04 北京当升材料科技股份有限公司 Method for preparing lithium battery positive electrode material
CN103022447B (en) * 2012-12-19 2015-08-19 苏州大学 The preparation method of serondary lithium battery negative pole Sn-Co-C composite material and serondary lithium battery
CN103985867B (en) * 2014-05-19 2016-08-24 电子科技大学 A kind of method preparing carbon cladding ferrosilite lithium composite material
CN104752073B (en) * 2015-04-15 2017-04-05 北京化工大学 A kind of preparation method of manganese iron axinite/carbon composite
CN105261738A (en) * 2015-10-20 2016-01-20 四川科能锂电有限公司 Preparation method of lithium iron phosphate
CN105789597A (en) * 2016-05-05 2016-07-20 天津巴莫科技股份有限公司 Preparation method of lithium vanadium phosphate cathode material
CN114824253B (en) * 2022-04-24 2024-03-15 中南大学 Granulating method for spherical particles of lithium ion battery anode material
CN116230888B (en) * 2023-02-17 2024-03-08 三一红象电池有限公司 Method for preparing carbon-coated sodium iron sulfate material, carbon-coated sodium iron sulfate material and battery

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