CN104091950A - Method for preparing lithium iron phosphate material with hydrothermal process - Google Patents
Method for preparing lithium iron phosphate material with hydrothermal process Download PDFInfo
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- CN104091950A CN104091950A CN201410347745.5A CN201410347745A CN104091950A CN 104091950 A CN104091950 A CN 104091950A CN 201410347745 A CN201410347745 A CN 201410347745A CN 104091950 A CN104091950 A CN 104091950A
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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
- H01M4/58—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
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- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/45—Phosphates containing plural metal, or metal and ammonium
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- 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
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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- Y02E60/10—Energy storage using batteries
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Abstract
The invention discloses a method for preparing a lithium iron phosphate material with a hydrothermal process, which comprises the following steps: (1) dissolving ferrous salt in a solvent and stirring uniformly; (2) adding water-soluble phosphate of lithium into the solution obtained in the step (1) and stirring uniformly; (3) adding an organic ignition-lost surfactant into the mixed liquid obtained in the step (2), and stirring uniformly; (4) performing hydrothermal reaction on the mixed liquid obtained in the step (3) at 150-250 DEG C; (5) repeatedly washing the precipitate obtained by the hydrothermal reaction, and drying the washed precipitate to obtain lithium iron phosphate precursor powder; and (6) grinding the dried lithium iron phosphate precursor powder, and calcining in an inert gas atmosphere at 500-800 DEG C. In the method disclosed by the invention, a lithium iron phosphate composite positive electrode material is synthesized with a one-step reaction process, the reaction steps are simplified, the product purity is improved, and the generation of some impurity phases is avoided; moreover, the morphology of the lithium iron phosphate composite positive electrode material can be effectively controlled, so that the problems that the material batch is unstable and the morphology cannot be controlled can be solved.
Description
Technical field
The present invention relates to the regulate and control method of lithium ferrous phosphate as anode material of lithium ion battery pattern, belong to electrode material preparation field.
Background technology
Lithium iron phosphate cathode material, due to nontoxic, environmental protection, security performance excellence and specific capacity advantages of higher, is considered to the first-selected positive electrode of power-type lithium ion battery of new generation.Along with the universal and popularization of electric automobile, lithium iron phosphate cathode material has been subject to paying close attention to widely and studying.But the lithium ion diffusion coefficient of lithium iron phosphate cathode material is little, and electronic conductivity is low, cause its cycle performance and high-rate charge-discharge capability at room temperature poor.The preparation method of at present conventional lithium iron phosphate cathode material mainly contains solid phase method and liquid phase method, and wherein solid phase method has carbothermic method, high-temperature solid phase reaction method, microwave process for synthesizing and pulsed laser deposition etc.; Liquid phase method has the precipitation method, sol-gel process, hydro thermal method and solvent-thermal method etc.The performance of lithium iron phosphate cathode material is somewhat dependent upon the appearance structure of material, therefore improves its chemical property by the pattern of regulation and control lithium iron phosphate cathode material and becomes particularly important.
Hydro thermal method belongs to wet method category, taking soluble ferrite, lithium salts and phosphoric acid as raw material, and direct synthesizing lithium ferrous phosphate under hydrothermal condition.The regulate and control method of lithium iron phosphate cathode material pattern is mainly the technological parameter by adjusting preparation method and adds surfactant (referring to patent documentation CN201210235708.6, CN201310170933.0 and " the pattern control of Hydrothermal Synthesis LiFePO 4 powder " at present, New Chemical Materials, 2008,36 (6), 74-75).But it is that product crystal formation is random that existing hydro thermal method is prepared LiFePO 4 technology major defect, and pattern generally cannot regulate and control, and purity is not high enough, usually generates ferric phosphate metastable phase, thereby affect the chemical property of material.Some are all directly to utilize the carbon source such as glucose, sucrose to carry out carbon to be coated with surfactant controlled material pattern method great majority, and in addition, the product great majority that said method prepares are all to have randomness, batch unsettled problem.
Summary of the invention
Prepare the defect of LiFePO 4 method for prior art, the present invention has improved the method that hydro thermal method is prepared LiFePO 4 composite positive pole, simplify reactions steps, emphasis regulates and controls the pattern of lithium iron phosphate cathode material by surfactant and carbon source, the crystallinity of products therefrom is better, pattern rule, product purity is also improved.
Method provided by the invention comprises:
(1) ferrous salt is dissolved in solvent, and stirs;
(2) phosphate of water miscible lithium joins in step (1) gained solution, and stirs;
(3) there is machine burning mistake type surfactant to join in step (2) gained mixed liquor by a certain proportion of, and stir;
(4) by step (3) gained mixed liquor 150-250 DEG C of hydro-thermal reaction;
(5), by the sediment cyclic washing obtaining after hydro-thermal reaction, the sediment after washing is dried and is obtained lithium iron phosphate precursor powder;
(6) the lithium iron phosphate precursor powder after oven dry grinds, and then 500-800 DEG C of calcining under inert gas atmosphere, obtains carbon cladded ferrous lithium phosphate composite positive pole.
Preferably, described step (1) also comprises in the solution of ferrous salt and adds organic reducing agent.
Described ferrous salt can be frerrous chloride, ferrous sulfate, ferrous nitrate, ferrous acetate, ferrous oxalate or vitamin C ferrous iron, and it can be also the hydrate of above-claimed cpd, or its mixture.
Preferably, described ferrous salt comprises ferrous sulfate, ferrous oxalate or ferrous acetate, or the hydrate of corresponding molysite.
Described organic reducing agent is the organic compound that a class well known in the art has reproducibility, and described organic reducing agent decomposes under sintering temperature and to produce at the most carbon residual or be dissolved in step (5) and wash solvent used.Described organic reducing agent preferred aldehydes base class organic substance (as acetaldehyde, glucose etc.), amino organic substance (as aniline, tyrosine etc.) and hydroxy kind organic substance (as vitamin C) etc.The addition of described organic reducing agent can be as required determined flexibly for those skilled in the art.
The solvent that described solvent uses for hydro-thermal reaction, preferred water.Preferably, the described preferred deionized water of solvent of step (1).
Preferably, described water miscible phosphate comprises one or more in lithium phosphate, lithium dihydrogen phosphate and phosphoric acid hydrogen two lithiums.
Described to have machine burning mistake type surfactant be the organic compound with reducing property, and it is residual under high-temperature roasting, to produce carbon, and then as the carbon source of LiFePO 4.Preferably, described in, there is machine burning mistake type surfactant to comprise one or more in citric acid, sodium alkyl benzene sulfonate class surfactant, alkyl ammonium bromide class surfactant, polyacrylamide, carboxymethyl cellulose class surfactant, sucrose and glucose.
Preferably, in the phosphate of described lithium, in lithium and step (1), in molysite, the mol ratio of iron is 0.95～1.05:1, and more preferably proportioning is 1:1..
Preferably, the mixing time of step (3) is 0.5～72h, and guarantee system stirs.For avoiding occurring can adopting the measures such as similar preservative film to seal isolated air by impurity in whipping process in product.
Preferably, the reaction time of described step (4) is 3-24 hour.
Preferably, the mol ratio that has ferrous ion in machine burning mistake type surfactant and ferrous salt described in is 0～2.5:1.
Preferred, described in to have the mol ratio of ferrous ion in machine burning mistake type surfactant and ferrous salt be 0.25～1.5:1.
Be more preferably, described in to have the mol ratio of ferrous ion in machine burning mistake type surfactant and ferrous salt be 0.5～1:1.
Preferably, the described cyclic washing of step (5) is by the sediment obtaining after hydro-thermal reaction deionized water and ethanol cyclic washing several, until washing lotion is limpid.
The present invention is in terms of existing technologies:
1. adopt the phosphate single step reaction synthesizing iron lithium phosphate material of ferrous salt and lithium, avoided traditional Lithium hydroxide monohydrate, phosphoric acid and three kinds of raw material reactions of ferrous sulfate heptahydrate and cause course of reaction complexity, intermediate product is more, gained end product purity is lower problem.
2., while reaction, by add organic reducing agent in reaction system, can prevent Fe in open system
2+be oxidized to Fe
3+thereby, effectively suppressed the generation of ferric phosphate dephasign.
3. add a certain proportion of surfactant, taking citric acid as example, it not only can serve as the conductivity of carbon source raising LiFePO 4 composite positive pole; Can also can impel as surfactant the crystalline growth of LiFePO 4, thereby improve the crystallinity of material, and impel the generation of the LiFePO 4 particle of regular pattern.
4. in step (3), burn the interpolation content of mistake type organic surface active agent and the length of mixing time by control, and then control the pattern of synthetic LiFePO 4 composite positive pole, further control appearance structure, particle size and the specific area of material.
Brief description of the drawings
Fig. 1 is to be 0.7g, the X-ray diffractogram that stirs LiFePO 4 composite positive pole prepared under 48 hours conditions at citric acid interpolation content.
Fig. 2 is at the X-ray diffractogram that does not add lithium iron phosphate cathode material prepared under citric acid, 48 hours conditions of stirring.
Fig. 3 is to be 1.4g, the X-ray diffractogram that stirs LiFePO 4 composite positive pole prepared under 48 hours conditions at citric acid interpolation content.
Fig. 4 is to be 2.1g, the X-ray diffractogram that stirs LiFePO 4 composite positive pole prepared under 3 hours conditions at citric acid interpolation content.
Fig. 5 is to be 4.2g, the X-ray diffractogram that stirs LiFePO 4 composite positive pole prepared under 48 hours conditions at citric acid interpolation content.
Fig. 6 is to be 6.3g, the X-ray diffractogram that stirs LiFePO 4 composite positive pole prepared under 48 hours conditions at citric acid interpolation content.
Fig. 7 is to be 0.7g, the scanning electron microscope diagram that stirs LiFePO 4 composite positive pole prepared under 48 hours conditions at citric acid interpolation content.
Fig. 8 is at the scanning electron microscope diagram that does not add lithium iron phosphate cathode material prepared under citric acid, 48 hours conditions of stirring.
Fig. 9 is to be 1.4g, the scanning electron microscope diagram that stirs LiFePO 4 composite positive pole prepared under 48 hours conditions at citric acid interpolation content.
Figure 10 is to be 2.1g, the scanning electron microscope diagram that stirs LiFePO 4 composite positive pole prepared under 3 hours conditions at citric acid interpolation content.
Figure 11 is to be 4.2g, the scanning electron microscope diagram that stirs LiFePO 4 composite positive pole prepared under 48 hours conditions at citric acid interpolation content.
Figure 12 is to be 6.3g, the scanning electron microscope diagram that stirs LiFePO 4 composite positive pole prepared under 48 hours conditions at citric acid interpolation content.
Embodiment
Below by part, embodiment is further elaborated the present invention, but it is not used in restriction content of the present invention.
Embodiment 1
1. take the ferrous sulfate heptahydrate of 5.56g and the bad acid of the anti-blood of 0.7g, be dissolved in 40mL deionized water, constantly carry out magnetic agitation until solution is light blue transparency liquid;
2. take 2.32g tricresyl phosphate lithium by ferrous sulfate heptahydrate and tricresyl phosphate lithium mol ratio 1:1, join step 1. in gained solution, stir;
3. the citric acid of 0.7g is joined to step 2. in gained mixed liquor, continue strong stirring 48 hours;
4. by step 3. gained mixed liquor move into autoclave, 180 DEG C of hydro-thermal reactions 8 hours;
5. by deionized water and ethanol cyclic washing several for the sediment obtaining after hydro-thermal reaction, until washing lotion is limpid; 80 DEG C of oven dry of sediment after washing 12 hours;
6. dry after gained powder grind, then under high-purity argon gas atmosphere 700 DEG C calcining 10 hours, obtain carbon cladded ferrous lithium phosphate composite positive pole.
Above-mentioned gained carbon cladded ferrous lithium phosphate composite positive pole is through XRD test (consulting Fig. 1), and product purity is higher, there is no the generation of impurity phase, and the crystallinity of material is higher; SEM test shows that (consulting Fig. 7) synthetic LiFePO 4 composite positive pole is the flower-like structure that oval nanometer sheet forms, and material has more regular pattern.
Comparative example 1
This comparative example is substantially the same manner as Example 1, and difference is, does not add citric acid in this comparative example.
The synthetic lithium iron phosphate cathode material of this comparative example is tested (consulting Fig. 2) through XRD, and product purity is higher, there is no the generation of impurity phase; But SEM test (consulting Fig. 8) shows that synthetic lithium iron phosphate cathode material does not have well-regulated pattern, and specific area is also lower.
Embodiment 2
The present embodiment 2 is substantially the same manner as Example 1, and difference is, in this embodiment, the addition of citric acid is 1.4g.
Above-mentioned gained carbon cladded ferrous lithium phosphate composite positive pole is through XRD test (consulting Fig. 3), and product purity is higher, there is no the generation of impurity phase, and the crystallinity of material is higher; SEM test shows that (consulting Fig. 9) synthetic LiFePO 4 composite positive pole is oval nanometer sheet, and material has more regular pattern, and particle size reduces, and specific area increases, and the dispersiveness of material also improves.
Embodiment 3
The present embodiment 3 is substantially the same manner as Example 1, and difference is, in this embodiment, the addition of citric acid is 2.1g, step 3. in mixing time become 3 hours.
Above-mentioned gained carbon cladded ferrous lithium phosphate composite positive pole is through XRD test (consulting Fig. 4), and product purity is higher, there is no the generation of impurity phase, and the crystallinity of material is higher; SEM test shows that (consulting Figure 10) synthetic LiFePO 4 composite positive pole is the sphere structure that stick phosphorus ferrous silicate lithium primary particle forms, material has more regular pattern, and material surface has compared with concrete dynamic modulus, be easy to the infiltration of electrolyte, thereby promote the embedding of lithium ion and the carrying out of deviating to react.In addition the dispersiveness of material also promotes to some extent.
Embodiment 4
The present embodiment 4 is substantially the same manner as Example 1, and difference is, in this embodiment, the addition of citric acid is 4.2g.
Above-mentioned gained carbon cladded ferrous lithium phosphate composite positive pole is through XRD test (consulting Fig. 5), and product purity is higher, there is no the generation of impurity phase, and the crystallinity of material is higher; SEM test shows that (consulting Figure 11) synthetic LiFePO 4 composite positive pole is block structure, and material has more regular pattern, and particle size increases to some extent, and specific area reduces relatively.
Embodiment 5
The present embodiment 2 is substantially the same manner as Example 1, and difference is, in this embodiment, the addition of citric acid is 6.3g.
Above-mentioned gained carbon cladded ferrous lithium phosphate composite positive pole is through XRD test (consulting Fig. 6), and product purity is higher, there is no the generation of impurity phase, and the crystallinity of material is higher; SEM test shows that (consulting Figure 12) synthetic LiFePO 4 composite positive pole is four prism type, and material has more regular pattern, and particle size continues to increase, and specific area reduces.
Can know by above-described embodiment, mixing time and surfactant have larger impact for technique effect of the present invention:
(1) impact of mixing time: the length of crystal growth cycle after the length major decision LiFePO 4 nucleation of mixing time, and then the size of decision primary particle.In embodiment 1-5 and comparative example 1, the mixing time of embodiment 3 is only 3 hours, other embodiment and comparative example are 48 hours, thereby in embodiment 3, after LiFePO 4 nucleation, do not carry out sufficient crystal growth, so primary particle size is all less than the primary particle (referring to the SEM figure contrast of the each embodiment synthesized of Fig. 7-Figure 12 LiFePO 4) of LiFePO 4 in other embodiment.
(2) impact of surfactant: surfactant not only can be controlled the dominant growth (with reference to table 1) of LiFePO 4 crystal face, and to a certain extent the size of crystal grain is also had a certain impact.In comparative example 1, do not add citric acid surfactant, thereby each crystal face of LiFePO 4 nucleus growth all do not control, cause final LiFePO 4 there is no regular morphology (as Fig. 8).In the time that citric acid interpolation content increases gradually, the dominant growth crystal face of LiFePO 4 can change, and power also changes relatively.In the time that citric acid interpolation content is 16.7%, all can there is dominant growth in crystal face (201) (111), (311) and (211) (020), be finally grown to the lithium iron phosphate particles (as Fig. 7) of flower-like structure; Be 33.4% when citric acid adds content, the dominant growth of crystal face (311) can highlight, and is better than significantly other crystal face, thereby finally LiFePO 4 particle is oval-shaped lamellar structure (as Fig. 9), and better dispersed; In the time that citric acid interpolation content is 50%, mixing time becomes 3 hours, and the time is shorter, thereby the dominant growth of each crystal face is relatively strong and weak not obvious, substantially be grown to corynebacterium primary particle, and then reunite for the LiFePO 4 (as Figure 10) of spherical structure; In the time that citric acid adds content continuation increase, crystal face (311) and (201) (111) dominant growth are comparatively outstanding, finally be grown to block structure (as Figure 11), or even long quadrangular structure (as Figure 12).
Table 1 LiFePO 4 crystal face dominant growth adds the variation of content with citric acid
Note: LiFePO 4 XRD main diffraction maximum position and crystal face corresponding relation: 20.8 ° (101); 25.7 ° of (201) (111); 29.8 ° of (211) (020); 35.7 ° (311).
Ferrous sulfate in above-described embodiment can also be frerrous chloride, ferrous oxalate or vitamin C ferrous iron, and it can be also the hydrate of above-claimed cpd; Described ascorbic acid can also be aldehyde radical type organic as acetaldehyde, glucose etc., amino organic substance is as aniline, tyrosine etc. and other hydroxy kind organic substances; In the time using closed system reaction, reducing agent also can not add.Described lithium phosphate can also be lithium dihydrogen phosphate and phosphoric acid hydrogen two lithiums, or the mixture of corresponding salt.Described citric acid can also be the tired surfactant of sodium alkyl benzene sulfonate, the tired surfactant of alkyl ammonium bromide, polyacrylamide, carboxymethyl cellulose class surfactant, sucrose and glucose, or one or more in respective compound (containing citric acid) composition.Before what respective compound played in invention act on, explain, test confirmation through inventor, it is similar using the technique effect of respective compound.
Claims (13)
1. hydro thermal method is prepared a method for ferrousphosphate lithium material, comprising:
(1) ferrous salt is dissolved in solvent, and stirs;
(2) phosphate of water miscible lithium joins in step (1) gained solution, and stirs;
(3) there is machine burning mistake type surfactant to join in step (2) gained mixed liquor by a certain proportion of, and stir;
(4) by step (3) gained mixed liquor 150-250 DEG C of hydro-thermal reaction;
(5), by the sediment cyclic washing obtaining after hydro-thermal reaction, the sediment after washing is dried and is obtained lithium iron phosphate precursor powder;
(6) the lithium iron phosphate precursor powder after oven dry grinds, and then 500-800 DEG C of calcining under inert gas atmosphere, obtains carbon cladded ferrous lithium phosphate composite positive pole.
2. method according to claim 1, is characterized in that, described step (1) also comprises in the solution of ferrous salt and adds organic reducing agent.
3. method according to claim 1 and 2, is characterized in that, described ferrous salt comprises one or more in frerrous chloride, ferrous sulfate, ferrous nitrate, ferrous acetate, ferrous oxalate or vitamin C ferrous iron.
4. method according to claim 2, is characterized in that, described organic reducing agent comprises one or more in aldehyde radical type organic, amino organic substance and hydroxy kind organic substance.
5. method according to claim 1 and 2, is characterized in that, the phosphate of described water miscible lithium comprises one or more in lithium phosphate, lithium dihydrogen phosphate and phosphoric acid hydrogen two lithiums.
6. method according to claim 1 and 2, is characterized in that, in the phosphate of described lithium, in lithium and step (1), in ferrous salt, the mol ratio of iron is 0.95～1.05:1.
7. method according to claim 1 and 2, it is characterized in that, described have machine burning mistake type surfactant to comprise one or more in citric acid, sodium alkyl benzene sulfonate class surfactant, alkyl ammonium bromide class surfactant, polyacrylamide, carboxymethyl cellulose class surfactant, sucrose and glucose.
8. method according to claim 1 and 2, is characterized in that, the mixing time of step (3) is 0.5～72h, and guarantee system stirs, and seals with preservative film in whipping process.
9. method according to claim 1 and 2, is characterized in that, the reaction time of described step (4) is 3-24 hour.
10. method according to claim 1 and 2, is characterized in that, the described cyclic washing of step (5) is by the sediment obtaining after hydro-thermal reaction deionized water and ethanol cyclic washing several, until washing lotion is limpid.
11. methods according to claim 10, is characterized in that, described in to have the mol ratio of ferrous ion in machine burning mistake type surfactant and ferrous salt be 0～2.5:1.
12. methods according to claim 11, is characterized in that, described in to have the mol ratio of ferrous ion in machine burning mistake type surfactant and ferrous salt be 0.25～1.5:1.
13. methods according to claim 12, is characterized in that, described in to have the mol ratio of ferrous ion in machine burning mistake type surfactant and ferrous salt be 0.5～1:1.
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Cited By (6)
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| CN107221672A (en) * | 2017-05-08 | 2017-09-29 | 陕西科技大学 | A kind of olive shape porous calcium phosphate iron lithium and preparation method thereof |
| CN109904409A (en) * | 2019-01-14 | 2019-06-18 | 广东工业大学 | A kind of lithium iron phosphate nano stick/graphene composite material and its preparation method and application |
| CN110480004A (en) * | 2019-08-29 | 2019-11-22 | 南京理工大学 | The method that hydro-thermal method prepares carbon-coated aluminum nanoparticles |
| CN110724820A (en) * | 2019-10-31 | 2020-01-24 | 华中科技大学 | Method for recycling decommissioned lithium ion battery anode material by using hydrothermal method |
| CN111900342A (en) * | 2020-06-18 | 2020-11-06 | 珠海冠宇电池股份有限公司 | Positive pole piece and preparation method and application thereof |
| CN113471420A (en) * | 2021-06-23 | 2021-10-01 | 绍兴铋华科技有限公司 | Bismuth tungstate coated lithium iron phosphate cathode material and preparation method thereof |
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| CN107221672A (en) * | 2017-05-08 | 2017-09-29 | 陕西科技大学 | A kind of olive shape porous calcium phosphate iron lithium and preparation method thereof |
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| CN109904409A (en) * | 2019-01-14 | 2019-06-18 | 广东工业大学 | A kind of lithium iron phosphate nano stick/graphene composite material and its preparation method and application |
| CN110480004A (en) * | 2019-08-29 | 2019-11-22 | 南京理工大学 | The method that hydro-thermal method prepares carbon-coated aluminum nanoparticles |
| CN110480004B (en) * | 2019-08-29 | 2021-11-09 | 南京理工大学 | Method for preparing carbon-coated nano aluminum powder by hydrothermal method |
| CN110724820A (en) * | 2019-10-31 | 2020-01-24 | 华中科技大学 | Method for recycling decommissioned lithium ion battery anode material by using hydrothermal method |
| CN110724820B (en) * | 2019-10-31 | 2021-05-18 | 华中科技大学 | Method for recycling decommissioned lithium ion battery anode material by using hydrothermal method |
| CN111900342A (en) * | 2020-06-18 | 2020-11-06 | 珠海冠宇电池股份有限公司 | Positive pole piece and preparation method and application thereof |
| CN113471420A (en) * | 2021-06-23 | 2021-10-01 | 绍兴铋华科技有限公司 | Bismuth tungstate coated lithium iron phosphate cathode material and preparation method thereof |
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Application publication date: 20141008 |