CN102751493A - Preparation method of lithium iron phosphate - Google Patents
Preparation method of lithium iron phosphate Download PDFInfo
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- CN102751493A CN102751493A CN2012102340441A CN201210234044A CN102751493A CN 102751493 A CN102751493 A CN 102751493A CN 2012102340441 A CN2012102340441 A CN 2012102340441A CN 201210234044 A CN201210234044 A CN 201210234044A CN 102751493 A CN102751493 A CN 102751493A
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- 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 belongs to a preparation method of a battery cathode material and particularly relates to a preparation method of lithium iron phosphate which has the characteristics that components between grains are similar, the granularity of the grains is uniform and the gram volume is high. A lithium salt, an iron salt, a doped metal element, a phosphate are prepared according to a molar ratio of lithium to iron to Mn<+> to phosphorus being 1: X: (1-X): 1 and the range of X is 0.9-1; the substances are mixed by ball milling and a conducting agent or a conducting agent precursor which is 0.5-10.0wt% of the generation amount of the lithium iron phosphate is added under the protection of inert gas to react to obtain the lithium iron phosphate. The preparation method of the lithium iron phosphate has the advantages that components between grains are similar, the granularity of the grains is uniform and the gram volume is high.
Description
Technical field
The invention belongs to the preparation method of cell positive material, it is close to be specifically related to each intergranular component of a kind of LiFePO4, and grain graininess is even, the method preparing phosphate iron lithium that gram volume is high.
Background technology
Along with various portable type electronic products are universal day by day; Battery receives publicity as a kind of power-supply device easy to carry day by day; China has become battery production and consumption big country; Contain heavy metal nickel, cadmium etc. in annual waste and old hydrogen nickel that produces and the ickel-cadmium cell environment is caused great pollution. face the whole world to the more and more stricter requirement of environmental protection; The development green energy resource is extremely urgent. and high performancely fill green lithium rechargeable battery, in various portable type electronic products and communication tool, be used widely in recent years, and progressively be developed as the electrical source of power of electric automobile. the performance of lithium ion battery and cost depend on positive electrode to a great extent; The every raising 50% of the specific capacity of positive electrode; The power density of battery can improve 28%, the every raising 50% of the specific capacity of negative material, and the power density of battery can improve 13% accordingly.The specific capacity of lithium ion battery negative material reaches the twice of positive electrode at present; The low bottleneck that has become the development of restriction lithium ion battery of positive electrode actual specific capacity; Therefore study anode material for lithium-ion batteries, have important practical significance for development and improvement lithium ion battery.Thereby the development of positive electrode becomes key.
The more positive electrode of research has LiCoO at present
2, LiNiO
2, LiMn
2O
4Deng.LiCoO
2Cost is higher and have toxicity; LiNiO
2There are safety issue and synthetic very difficulty; LiMn
2O
4Cycle performance and high-temperature behavior still need bigger improvement.And as the rhombic system olivine-type LiFePO of new type lithium ion battery positive electrode
4Then have the advantage of above-mentioned various materials concurrently; Particularly iron resource is abundant, it is cheap, Heat stability is good, environmentally safe; Fe has aboundresources, cost is low and advantage such as avirulence; People extremely pay close attention to as the research of anode material for lithium-ion batteries iron containing compounds in recent years, LiFePO
4Positive electrode has become one of focus of research.
Yet, LiFePO
4The tightly packed mode of atom has caused the diffusion coefficient of lithium ion and ionic conductivity lower in the crystal, and big electric current charge and discharge performance is also relatively poor.Therefore, the big electric current charge and discharge of diffusion coefficient, ionic conductivity and the improvement performance that how to improve lithium ion is LiFePO
4As anode active material of lithium ion battery practicability problem demanding prompt solution.People improve the conductivity of LiFePO4 through the whole bag of tricks, and have obtained major progress.Corrective measure mainly concentrates on doping and the surface modification and comprises:
1, granule interior is mixed conductive carbon material or conductive metal particle in the LiFePO4, perhaps toward LiFePO4 particle surface coated with conductive material with carbon element or conducting metal, improves the electronic conductivity of material.
2, in LiFePO4, mix the metal ion of impurity at high price, like Mg
2+, Al
3+, Cr
2+, Ti
4+Deng.Replace a part of Li
+Or Fe
2+The position, thereby make the LiFePO4 intrinsic semiconductor be transformed into n type or p N-type semiconductor N, can conductivity of electrolyte materials be improved 8 one magnitude.
LiFePO
4Theoretical capacity be 170mAh/g, its electrochemical reaction is at LiFePO
4And FePO
4Two alternate carrying out.Prepare LiFePO at present
4The main synthetic method of powder is a solid sintering technology, in addition, also has hydro thermal method, sol-gal process etc.Wherein solid-phase synthesis is the most ripe method, and this method is simple and convenient, easy operating.But directly calcining after the solid phase method reactant mixes in dry method or liquid phase usually; Various raw material particles contact with the mode of piling up, and contact defective tightness, various elements are difficult to even diffused in calcination process; So that each the intergranular component of LiFePO4 that synthesizes differs bigger; Effectively synthetic ratio is lower, and finished particle is inhomogeneous, and product capacity is on the low side.
Summary of the invention
The objective of the invention is to overcome defective of the prior art and provide each intergranular component of a kind of LiFePO4 close, grain graininess is even, the method preparing phosphate iron lithium that gram volume is high.
The objective of the invention is to realize like this: the present invention includes following steps:
One, lithium salts, molysite, doped metallic elements, phosphate are pressed lithium, iron, M
N+, phosphorus mol ratio be 1: X: (1-X): 1 ratio is carried out proportioning, and the scope of described X is 0.9-1;
Two, with the ball mill mixing in batch mixer of the mixed material in the step 1, the temperature during said ball mill mixing is 20-50 ℃, and ratio of grinding media to material 1-3, batch mixer rotating speed are 10-30r/min, dry ball milling mixing 1-10 hour;
Three, make that mixed material carries out preliminary treatment in the step 2 under inert gas shielding, naturally cool to room temperature after the preliminary treatment, temperature range is 400-600 ℃ during described preliminary treatment, and the pretreated time is 8-24 hour;
Four, in step 3, add one of the conductive agent account for LiFePO4 growing amount 0.5wt.%-10.0wt.% or conductive agent predecessor;
Five, the mixing of materials in the step 4 is pulverized, be crushed to D
50Between 1-5 μ m;
Six, make the material after pulverizing in the step 5 under inert gas shielding, carry out the constant temperature processing, constant temperature naturally cools to room temperature after handling, and temperature range was 650-750 ℃ when described constant temperature was handled, and the time that constant temperature is handled is 8-24 hour;
Seven, the material that is cooled to room temperature in the step 6 being pulverized is 250 orders, is finished product.
Lithium salts in the described step 1 is selected from one of lithium carbonate or lithium hydroxide.Molysite in the described step 1 is selected from ferrous oxalate, ferrous acetate, one of ferric nitrate and iron oxide.Phosphate in the described step 1 is selected from one of ammonium dihydrogen phosphate or diammonium hydrogen phosphate.Doped metallic elements in the described step 1 is selected from manganese, magnesium, titanium, aluminium, niobium, chromium, one or more in zinc or the rare earth element.Conductive agent is selected from one or more of native graphite, Delanium, nanometer metallic silver, nano-metallic copper, conductive carbon black and organic matter pyrolysis charcoal in the described step 4.Described organic matter pyrolysis charcoal is selected from polyvinyl alcohol, butadiene-styrene rubber breast, carboxymethyl cellulose, polystyrene, polymethyl methacrylate, polytetrafluoroethylene, polyacrylonitrile, phenolic resins, epoxy resin, glucose, sucrose, fructose, cellulose; One of starch or pitch are presoma, through the formed pyrolytic carbon of high temperature cabonization.Inert gas in described step 4 and the step 7 is argon gas, nitrogen, one of helium or neon.The overall control that adds conductive agent or conductive agent predecessor in the described step 4 should guarantee that conductive agent final residue amount accounts for the 0.5wt.%-10.0wt.% of LiFePO4 product amount.The conductive agent predecessor is selected from vinyl alcohol, butadiene-styrene rubber breast, carboxymethyl cellulose, polystyrene, polymethyl methacrylate, polytetrafluoroethylene, polyacrylonitrile, phenolic resins, epoxy resin, glucose, sucrose, fructose, cellulose, one or more in starch or the pitch in the described step 4.
The used equipment of dry ball milling is the inclined batch mixer that possesses jar interior temperature controlled function, anistree mill among the present invention; One of bipyramid batch mixer or conical mixer; Used mill is situated between and is alumina balls, zirconia ball, one of agate ball or stainless steel ball, and sphere diameter is at 5-50mm.Preliminary treatment and constant temperature are handled and are adopted push-plate type tunnel cave, tube furnace, bell jar stove, rotary furnace, steel band stove, vacuum furnace, one of sealed type or cyclone furnace kiln among the present invention; Said reducing mechanism adopts wet stirring mill, circulating ultra-fine mill, ultra-fine sand milling, inclined batch mixer, anistree mill, bipyramid batch mixer, conical mixer; One of mechanical type pulverizer or compound pulverizer; Used mill is situated between and is alumina balls, zirconia ball, agate ball or stainless steel ball, and sphere diameter is at 5-50mm.
The present invention compares with other synthetic methods: it is huge that the synthetic common used raw material of LiFePO4 are in the pressed powder course of reaction diffusion couple reaction result influence evenly and rapidly of various elements, main through refinement feed particles granularity with increase by two kinds of approach solutions of exposure level diffusion problem between the raw material in the building-up process.Traditional method is that dispersant carries out wet grinding mixing and common dry mixed with alcohol, and the contact between the raw material is physics and piles up contact, and contact area is little and unstable.Raw material is in mixed process among the present invention; Through factors such as control mixing temperature, time, ratios of grinding media to material; In the time of refinement feed particles granularity, utilize the chemical reaction that takes place between the lithium salts of phosphate acid in the raw material and alkalescence, make between the various raw materials and merge; Reduce the purpose that closely contacts between the raw material thereby reach the raw material grain graininess.Thereby product efficiency of the present invention is higher, and gram volume can reach 165mAh/g, is higher than the 160mAh/g of conventional method.The present invention is a dry ball milling, and the wet ball grinding with respect to generally adopting does not use alcohol in the mechanical milling process, do not need behind the ball milling material is carried out dried, has reduced production cost.
It is close that the present invention has each intergranular component of LiFePO4, and grain graininess is even, the advantage that gram volume is high.
Description of drawings
Fig. 1 is a particle size distribution figure of the present invention.
Fig. 2 is an XRD figure of the present invention.
Fig. 3 is 0.1C charging and discharging curve figure of the present invention.
Embodiment
Like Fig. 1,2, shown in 3, the step that the present invention includes is following:
One, lithium salts, molysite, doped metallic elements, phosphate are pressed lithium, iron, M
N+, phosphorus mol ratio be 1: X: (1-X): 1 ratio is carried out proportioning, and the scope of described X is 0.9-1;
Two, with the ball mill mixing in batch mixer of the mixed material in the step 1, the temperature during said ball mill mixing is 20-50 ℃, and ratio of grinding media to material 1-3, batch mixer rotating speed are 10-30r/min, dry ball milling mixing 1-10 hour;
Three, make that mixed material carries out preliminary treatment in the step 2 under inert gas shielding, naturally cool to room temperature after the preliminary treatment, temperature range is 400-600 ℃ during described preliminary treatment, and the pretreated time is 8-24 hour;
Four, in step 3, add one of the conductive agent account for LiFePO4 growing amount 0.5wt.%-10.0wt.% or conductive agent predecessor;
Five, the mixing of materials in the step 4 is pulverized, be crushed to D
50Between 1-5 μ m;
Six, make the material after pulverizing in the step 5 under inert gas shielding, carry out the constant temperature processing, constant temperature naturally cools to room temperature after handling, and temperature range was 650-750 ℃ when described constant temperature was handled, and the time that constant temperature is handled is 8-24 hour;
Seven, the material that is cooled to room temperature in the step 6 being pulverized is 250 orders, is finished product.
Lithium salts in the described step 1 is selected from one of lithium carbonate or lithium hydroxide.Molysite in the described step 1 is selected from ferrous oxalate, ferrous acetate, one of ferric nitrate and iron oxide.Phosphate in the described step 1 is selected from one of ammonium dihydrogen phosphate or diammonium hydrogen phosphate.Doped metallic elements in the described step 1 is selected from manganese, magnesium, titanium, aluminium, niobium, chromium, one or more in zinc or the rare earth element.Conductive agent is selected from one or more of native graphite, Delanium, nanometer metallic silver, nano-metallic copper, conductive carbon black and organic matter pyrolysis charcoal in the described step 4.Described organic matter pyrolysis charcoal is selected from polyvinyl alcohol, butadiene-styrene rubber breast, carboxymethyl cellulose, polystyrene, polymethyl methacrylate, polytetrafluoroethylene, polyacrylonitrile, phenolic resins, epoxy resin, glucose, sucrose, fructose, cellulose; One of starch or pitch are presoma, through the formed pyrolytic carbon of high temperature cabonization.Inert gas in described step 4 and the step 7 is argon gas, nitrogen, one of helium or neon.The overall control that adds conductive agent or conductive agent predecessor in the described step 4 should guarantee that conductive agent final residue amount accounts for the 0.5wt.%-10.0wt.% of LiFePO4 product amount.The conductive agent predecessor is selected from vinyl alcohol, butadiene-styrene rubber breast, carboxymethyl cellulose, polystyrene, polymethyl methacrylate, polytetrafluoroethylene, polyacrylonitrile, phenolic resins, epoxy resin, glucose, sucrose, fructose, cellulose, one or more in starch or the pitch in the described step 4.
Explanation the present invention for detailed enumerates following examples and describes, but the present invention is not limited to these embodiment.
Embodiment 1
One, be 1: 0.9: 0.1 with lithium hydroxide, ferrous acetate, magnesium hydroxide, diammonium hydrogen phosphate in the mol ratio of lithium, iron, magnesium, phosphorus: 1 ratio is carried out proportioning; Lithium hydroxide 22.45Kg, ferrous acetate 147.62Kg, magnesium hydroxide 5.50Kg, diammonium hydrogen phosphate 124.43Kg;
Two, with the ball mill mixing in 2000L inclined batch mixer of the mixed material in the step 1, the temperature during said ball mill mixing is 20 ℃, ratio of grinding media to material 3, and the batch mixer rotating speed is 10r/min, dry ball milling mixed 10 hours;
Three, make that mixed material carries out preliminary treatment in the step 2 in rotary furnace under nitrogen protection, naturally cool to room temperature after the preliminary treatment, temperature is 400 ℃ during described preliminary treatment, and the pretreated time is 24 hours;
Four, in step 3, add glucose 15Kg;
Five, mixing of materials in the step 4 is pulverized, be crushed to D
50Between 1-5 μ m;
Six, make in the step 5 material after pulverizing under nitrogen protection, carry out constant temperature in the meshbeltfurnace and handle, constant temperature naturally cools to room temperature after handling, and temperature was 650 ℃ when described constant temperature was handled, and the time that constant temperature is handled is 24 hours;
Seven, the material that is cooled to room temperature in the step 6 being pulverized is 250 orders, obtains the 150Kg finished product.
One, be that 1: 1: 1 ratio is carried out proportioning, lithium carbonate 44.37Kg, iron oxide 96.58Kg, diammonium hydrogen phosphate 159.36Kg with lithium carbonate, iron oxide, diammonium hydrogen phosphate in the mol ratio of lithium, iron, phosphorus;
Two, with the ball mill mixing in the anistree mill of 2000L of the mixed material in the step 1, the temperature during said ball mill mixing is 50 ℃, ratio of grinding media to material 1, and the batch mixer rotating speed is 10r/min, dry ball milling mixed 1 hour;
Three, make that mixed material carries out preliminary treatment in the step 2 in the pusher furnace under nitrogen protection, naturally cool to room temperature after the preliminary treatment, temperature is 600 ℃ during described preliminary treatment, and the pretreated time is 8 hours;
Four, in step 3, add acetylene black 2.5Kg;
Five, with material in the step 4 in stirring mill, be that dispersant grinds with alcohol, be crushed to D
50Between 1-5 μ m, mix the extremely alcohol-free of slurry through vacuumize.
Six, make in the step 5 material after pulverizing under nitrogen protection, the steel band stove carries out constant temperature to be handled, and constant temperature naturally cools to room temperature after handling, and temperature was 750 ℃ when described constant temperature was handled, and the time that constant temperature is handled is 8 hours;
Seven, the material that is cooled to room temperature in the step 6 being pulverized is 250 orders, obtains the 150Kg finished product.
One, be 1: 0.98: 0.02 with lithium carbonate, ferrous oxalate, manganese dioxide, ammonium dihydrogen phosphate in the mol ratio of lithium, iron, manganese, phosphorus: 1 ratio is carried out proportioning; Lithium carbonate 33.45Kg, ferrous oxalate 160.43Kg, magnesium hydroxide 1.57Kg, ammonium dihydrogen phosphate 104.65Kg;
Two, with the ball mill mixing in 2000L bipyramid mill of the mixed material in the step 1, the temperature during said ball mill mixing is 30 ℃, ratio of grinding media to material 2, and the batch mixer rotating speed is 20r/min, dry ball milling mixed 3 hours;
Three, make that mixed material carries out preliminary treatment in the step 2 in the rotary furnace under nitrogen protection, naturally cool to room temperature after the preliminary treatment, temperature is 500 ℃ during described preliminary treatment, and the pretreated time is 12 hours;
Four, in step 3, add acetylene black 1.5Kg, sucrose 12Kg;
Five, with material in the step 4 in sand mill, be that dispersant grinds with alcohol, be crushed to D
50Between 1-5 μ m, mix the extremely alcohol-free of slurry through vacuumize.
Six, make in the step 5 material after pulverizing under nitrogen protection, carry out constant temperature in the steel band stove and handle, constant temperature naturally cools to room temperature after handling, and temperature was 700 ℃ when described constant temperature was handled, and the time that constant temperature is handled is 12 hours;
Seven, the material that is cooled to room temperature in the step 6 being pulverized is 250 orders, obtains the 150Kg finished product.
Claims (10)
1. method preparing phosphate iron lithium, it is characterized in that: its step is following:
One, lithium salts, molysite, doped metallic elements, phosphate are pressed lithium, iron, M
N+, phosphorus mol ratio be 1: X: (1-X): 1 ratio is carried out proportioning, and the scope of described X is 0.9-1;
Two, with the ball mill mixing in batch mixer of the mixed material in the step 1, the temperature during said ball mill mixing is 20-50 ℃, and ratio of grinding media to material 1-3, batch mixer rotating speed are 10-30r/min, dry ball milling mixing 1-10 hour;
Three, make that mixed material carries out preliminary treatment in the step 2 under inert gas shielding, naturally cool to room temperature after the preliminary treatment, temperature range is 400-600 ℃ during described preliminary treatment, and the pretreated time is 8-24 hour;
Four, in step 3, add one of the conductive agent account for LiFePO4 growing amount 0.5wt.%-10.0wt.% or conductive agent predecessor;
Five, the mixing of materials in the step 4 is pulverized, be crushed to D
50Between 1-5 μ m;
Six, make the material after pulverizing in the step 5 under inert gas shielding, carry out the constant temperature processing, constant temperature naturally cools to room temperature after handling, and temperature range was 650-750 ℃ when described constant temperature was handled, and the time that constant temperature is handled is 8-24 hour;
Seven, the material that is cooled to room temperature in the step 6 being pulverized is 250 orders, is finished product.
2. method preparing phosphate iron lithium according to claim 1 is characterized in that: the lithium salts in the described step 1 is selected from one of lithium carbonate or lithium hydroxide.
3. method preparing phosphate iron lithium according to claim 1 is characterized in that: the molysite in the described step 1 is selected from ferrous oxalate, ferrous acetate, one of ferric nitrate and iron oxide.
4. method preparing phosphate iron lithium according to claim 1 is characterized in that: the phosphate in the described step 1 is selected from one of ammonium dihydrogen phosphate or diammonium hydrogen phosphate.
5. method preparing phosphate iron lithium according to claim 1 is characterized in that: the doped metallic elements in the described step 1 is selected from manganese, magnesium, titanium, aluminium, niobium, chromium, one or more in zinc or the rare earth element.
6. method preparing phosphate iron lithium according to claim 1 is characterized in that: conductive agent is selected from one or more of native graphite, Delanium, nanometer metallic silver, nano-metallic copper, conductive carbon black and organic matter pyrolysis charcoal in the described step 4.
7. method preparing phosphate iron lithium according to claim 6; It is characterized in that: described organic matter pyrolysis charcoal is selected from polyvinyl alcohol, butadiene-styrene rubber breast, carboxymethyl cellulose, polystyrene, polymethyl methacrylate, polytetrafluoroethylene, polyacrylonitrile, phenolic resins, epoxy resin, glucose, sucrose, fructose, cellulose; One of starch or pitch are presoma, through the formed pyrolytic carbon of high temperature cabonization.
8. according to the described method preparing phosphate iron lithium of claim 1, it is characterized in that: the inert gas in described step 4 and the step 7 is argon gas, nitrogen, one of helium or neon.
9. method preparing phosphate iron lithium according to claim 1 is characterized in that: the overall control that adds conductive agent or conductive agent predecessor in the described step 4 should guarantee that conductive agent final residue amount accounts for the 0.5wt.%-10.0wt.% of LiFePO4 product amount.
10. method preparing phosphate iron lithium according to claim 1; It is characterized in that: the conductive agent predecessor is selected from vinyl alcohol, butadiene-styrene rubber breast, carboxymethyl cellulose, polystyrene, polymethyl methacrylate, polytetrafluoroethylene, polyacrylonitrile, phenolic resins, epoxy resin, glucose, sucrose, fructose, cellulose, one or more in starch or the pitch in the described step 4.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103346317A (en) * | 2013-07-01 | 2013-10-09 | 金瑞新材料科技股份有限公司 | Compound doped and cladded lithium ion cell anode material LiFePO4 and preparation method thereof |
| CN103985861A (en) * | 2014-04-03 | 2014-08-13 | 恒正科技（苏州）有限公司 | Electrochemically active positive electrode material and preparation method thereof |
| CN106229505A (en) * | 2016-08-17 | 2016-12-14 | 深圳市贝特瑞纳米科技有限公司 | A kind of high-density spherical nano lithium iron phosphate material and preparation method thereof and the lithium ion battery comprising it |
| CN107994223A (en) * | 2017-12-11 | 2018-05-04 | 广东工业大学 | A kind of composite material of the fluorin-doped modification of aluminium and its preparation method and application |
| CN108400330A (en) * | 2018-03-08 | 2018-08-14 | 蒋央芳 | A kind of preparation method of carbon doping phosphoric acid manganese (III) |
| CN108565428A (en) * | 2018-04-19 | 2018-09-21 | 零零二信息科技（沧州）有限责任公司 | Improve lithium ion battery LiFePO4The method of composite positive pole performance |
| CN108878874A (en) * | 2017-10-13 | 2018-11-23 | 久兆新能源科技股份有限公司 | A kind of lithium iron phosphate positive material and anode pole piece of homogeneous grain diameter |
| CN111186828A (en) * | 2020-01-16 | 2020-05-22 | 昆明理工大学 | Preparation method of metal-doped lithium iron phosphate |
| CN112786859A (en) * | 2021-01-22 | 2021-05-11 | 合肥国轩高科动力能源有限公司 | Preparation method of tantalum-doped/porous metal nanoparticle-coated modified lithium iron phosphate material |
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103346317A (en) * | 2013-07-01 | 2013-10-09 | 金瑞新材料科技股份有限公司 | Compound doped and cladded lithium ion cell anode material LiFePO4 and preparation method thereof |
| CN103346317B (en) * | 2013-07-01 | 2015-10-28 | 金瑞新材料科技股份有限公司 | Composite mixed and cladded type anode material for lithium-ion batteries LiFePO 4and preparation method thereof |
| CN103985861A (en) * | 2014-04-03 | 2014-08-13 | 恒正科技（苏州）有限公司 | Electrochemically active positive electrode material and preparation method thereof |
| CN103985861B (en) * | 2014-04-03 | 2016-05-18 | 苏州工业园区日高能源科技有限公司 | A kind of electro-chemical activity positive electrode and preparation method thereof |
| CN106229505B (en) * | 2016-08-17 | 2019-10-25 | 深圳市贝特瑞纳米科技有限公司 | A kind of high-density spherical nano lithium iron phosphate material and preparation method thereof and lithium ion battery comprising it |
| CN106229505A (en) * | 2016-08-17 | 2016-12-14 | 深圳市贝特瑞纳米科技有限公司 | A kind of high-density spherical nano lithium iron phosphate material and preparation method thereof and the lithium ion battery comprising it |
| CN108878874A (en) * | 2017-10-13 | 2018-11-23 | 久兆新能源科技股份有限公司 | A kind of lithium iron phosphate positive material and anode pole piece of homogeneous grain diameter |
| CN107994223A (en) * | 2017-12-11 | 2018-05-04 | 广东工业大学 | A kind of composite material of the fluorin-doped modification of aluminium and its preparation method and application |
| CN108400330A (en) * | 2018-03-08 | 2018-08-14 | 蒋央芳 | A kind of preparation method of carbon doping phosphoric acid manganese (III) |
| CN108400330B (en) * | 2018-03-08 | 2020-07-14 | 蒋央芳 | Preparation method of carbon-doped manganese (III) phosphate |
| CN108565428A (en) * | 2018-04-19 | 2018-09-21 | 零零二信息科技（沧州）有限责任公司 | Improve lithium ion battery LiFePO4The method of composite positive pole performance |
| CN111186828A (en) * | 2020-01-16 | 2020-05-22 | 昆明理工大学 | Preparation method of metal-doped lithium iron phosphate |
| CN112786859A (en) * | 2021-01-22 | 2021-05-11 | 合肥国轩高科动力能源有限公司 | Preparation method of tantalum-doped/porous metal nanoparticle-coated modified lithium iron phosphate material |
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Application publication date: 20121024 |