CN104733709A - Preparation method of lithium manganese iron phosphate or lithium manganese iron phosphate composite material in controllable crystal form - Google Patents

Preparation method of lithium manganese iron phosphate or lithium manganese iron phosphate composite material in controllable crystal form Download PDF

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Publication number
CN104733709A
CN104733709A CN201410804443.6A CN201410804443A CN104733709A CN 104733709 A CN104733709 A CN 104733709A CN 201410804443 A CN201410804443 A CN 201410804443A CN 104733709 A CN104733709 A CN 104733709A
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lithium
polyethylene glycol
preparation
manganese phosphate
iron phosphate
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王强
秦尚伟
郭庆山
马忠贺
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YINGKOU HANGSHENG SCIENCE & TECHNOLOGY INDUSTRY Co Ltd
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YINGKOU HANGSHENG SCIENCE & TECHNOLOGY INDUSTRY Co Ltd
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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
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Composite Materials (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention provides a preparation method of lithium manganese iron phosphate or lithium manganese iron phosphate composite material in a controllable crystal form. The method comprises the following steps: 1, mixing polyethylene glycol and water according to a certain volume ratio; sequentially adding phosphoric acid and lithium hydroxide, wherein the molar ratio of P to Li is 1: 3; dropwise adding a lithium hydroxide solution to adjust the pH value of the mixed solution; then, adding a manganese source and an iron source, wherein the molar ratio of Mn to Fe to P is equal to x: (1-x): 1, and x is more than or equal to 0.5 and less than 1; 2, carrying out a hydrothermal reaction for 3-15 hours at the temperature of 150-220 DEG C; by the end of the reaction, cooling, filtering, washing and drying to obtain lithium manganese iron phosphate LiMnxFe1-xPO4, wherein x is more than or equal to 0.5 and less than 1; 3, after carbon-coating, roasting for 2-8 hours in an inert atmosphere furnace with the temperature of 550-750 DEG C to finally obtain the lithium manganese iron phosphate/carbon composite cathode material, wherein the carbon content is 2.0-3.0wt%. The technological method is simple and controllable; the prepared lithium manganese iron phosphate/ carbon composite cathode material is high in specific capacity and good in cycle performance; the product is controllable in crystal form, and the composition and the structure of the product are uniform.

Description

The preparation method of the iron manganese phosphate for lithium that a kind of crystal formation is controlled or its composite material
Technical field
The present invention relates to the preparation method of electrode material, particularly relate to the preparation of the controlled iron manganese phosphate for lithium of crystal formation or its composite material.
Background technology
The phosphate-based positive electrode of novel olivine-type structure is better than traditional Layered Structural Positive Electrode Materials (as cobalt acid lithium, lithium nickelate, ternary material), its representative materials LiFePO4 (LiFePO in security performance and cycle life etc. 4) extensively studied confirmation by academia and industrial circle, and be widely used in the field such as power and energy-storage battery.But, LiFePO4 3.4V (Li/Li +) current potential limit the lifting of battery energy density, therefore lithium iron phosphate dynamic battery market development is limited.Compared with LiFePO4, iron manganese phosphate for lithium has high potential and almost identical theoretical capacity, under the condition that equivalent capability plays, the energy density of iron manganese phosphate lithium battery will improve a lot than ferric phosphate lithium cell, battery energy density can be made to be promoted to 150Wh/kg by current 90Wh/kg, the benefit brought is exactly the increase of electric motor car course continuation mileage, therefore, in the world iron manganese phosphate for lithium is classified as high-energy-density power lithium-ion battery positive electrode of new generation.In addition, the manganese element aboundresources in lithium iron manganese phosphate anode material, is conducive to the production cost reducing material.
Although it is high that iron manganese phosphate for lithium novel battery material has voltage, the advantages such as battery energy density is high, self also there is a lot of problem in it: the poor electric conductivity of (1) material; (2) specific capacity is not high bad with cycle performance.Once the research and development of this new material make a breakthrough, it can not only seize the market share of LiFePO4, and can extrude the market space of LiMn2O4 and ternary material, breaks the market structure of positive electrode current material.
At present, the conventional synthetic method of synthesizing iron manganese phosphate for lithium mainly contains: high temperature solid-state method, sol-gal process, microwave method, hydro thermal method etc.The advantage of hydro thermal method is that synthesis temperature is low, the composition of product and even structure, diameter of particle is less, process is simple, equipment and process is simple and carry out in closed container, do not need to use inert gas to make protective gas, greatly reduces cost.
Summary of the invention
For solving the poor electric conductivity of iron manganese phosphate lithium material, problem, the iron manganese phosphate for lithium providing a kind of crystal formation controlled and the preparations of composite material thereof such as the not high and cycle performance of specific capacity is bad.Specifically by the following technical solutions:
(1) polyethylene glycol is mixed with the volume ratio of water by 1:1-10, in Aqueous Solutions of Polyethylene Glycol, add phosphoric acid, fully add lithium hydroxide again, wherein mol ratio Li:P=3:1 after mixing, after question response is complete; Add lithium hydroxide solution, regulate ph value of mixture=11-13; Manganese source and ferrous source is added again, mol ratio Mn:Fe:P=x:(1-x in mixed liquor): 1, (0.5≤x < 1);
(2) step (1) gained mixed liquor is gone in water heating kettle, by water heating kettle constant temperature 3-15h at the temperature of 150-220 DEG C, reacted rear cooling, after filtration, wash and drying, be iron manganese phosphate for lithium LiMn xfe 1-xpO 4, 0.5≤x < 1;
(3) after precursor carbon step (2) obtained is coated in the inert atmosphere stove of 550-750 DEG C constant temperature 2-8h, finally obtain manganese phosphate lithium/carbon composite material LiMn xfe 1-xpO 4/ C.
Polyethylene glycol described in step of the present invention (1) is one or two or more kinds in polyethylene glycol (200), polyethylene glycol (300), polyethylene glycol (400) and polyethylene glycol (600).
Lithium hydroxide solution mass concentration described in step of the present invention (1) is 6%.
Reacting completely described in step of the present invention (1) refers to the temperature return room temperature of mixed liquor, and the reaction time is generally 15-50min.
The coated process of carbon iron manganese phosphate for lithium used described in step of the present invention (3) and the mass ratio of carbon source are 4-12:1.
Step of the present invention (3) described manganese phosphate lithium/carbon composite material LiMn xfe 1-xpO 4carbon content in/C is 2.0-3.0wt%.
Manganese source of the present invention is selected from one in manganese chloride or manganese sulfate or two kinds; Ferrous source is selected from one in frerrous chloride or ferrous sulfate or two kinds.
Step of the present invention (3) described carbon source is one in sucrose, glucose, citric acid, polyethylene glycol or two kinds.
Compared to prior art, beneficial effect of the present invention:
1, the polyethylene glycol used in method provided by the invention be mean molecule quantity about 200 at least 6000 the general name of ethylene glycol high polymer, there is good water-soluble, excellent dispersiveness and cementability.Choose polyethylene glycol as the structure directing agent preparing iron manganese phosphate for lithium, be because it can the growth of control lattice effectively in hydro-thermal reaction, conclusive help is risen to the chemical property of material; There is good peptizaiton simultaneously.In comparative example 1, utilize separately water to prepare iron manganese phosphate for lithium as solvent, the chemical property extreme difference of the material obtained, and particle diameter is larger; In comparative example 2, utilized ethylene glycol to prepare iron manganese phosphate for lithium and composite material thereof, the chemical property of the material obtained can not show a candle to the material utilizing polyethylene glycol to prepare, and particle diameter is also larger.
2, the carbon content of iron manganese phosphate for lithium/carbon composite anode material that method provided by the invention is prepared is 2.0-3.0wt%, compared with the material prepared, has lower carbon content, improve the volume energy density of material to a certain extent with additive method.
3, iron manganese phosphate for lithium/carbon composite anode material that hydro thermal method provided by the invention is prepared has higher specific capacity and preferably cycle performance.
Accompanying drawing explanation
Fig. 1 is the capacity under the iron manganese phosphate for lithium electrode material different multiplying of embodiment 1 preparation and the cycle performance under 0.5C multiplying power.
Fig. 2 is the X-ray spectrogram of iron manganese phosphate for lithium electrode material prepared by embodiment 1.Abscissa is 2 θ angles, and ordinate represents the intensity size at peak.
Fig. 3 is the scanning electron microscope (SEM) photograph (20 μm) of iron manganese phosphate for lithium electrode material prepared by embodiment 1.
Fig. 4 is the scanning electron microscope (SEM) photograph (10 μm) of iron manganese phosphate for lithium electrode material prepared by embodiment 1.
Fig. 5 is the scanning electron microscope (SEM) photograph (20 μm) of iron manganese phosphate for lithium electrode material prepared by comparative example 1.
Fig. 6 is the scanning electron microscope (SEM) photograph (20 μm) of iron manganese phosphate for lithium electrode material prepared by comparative example 2.
Embodiment
Embodiment 1
By polyethylene glycol (400) with water by volume for 1:3 mixes, first in polyethylene glycol (400) aqueous solution, add phosphoric acid, lithium hydroxide is added again after abundant mixing, wherein mol ratio is Li:P=3:1, after 30min reacts completely, add the lithium hydroxide solution that mass concentration is 6%, make the pH value of mixed liquor reach 12.5; In mixed liquor, add manganese sulfate and ferrous sulfate again, mol ratio is Mn:Fe:P=0.5:0.5:1; Mixed liquor is gone in water heating kettle, by its constant temperature 12h at the temperature of 180 DEG C, after having reacted, reactor is taken out, open after at room temperature naturally cooling, after filtration, wash, and dry at 80 DEG C of temperature, be iron manganese phosphate for lithium LiMn 0.5fe 0.5pO 4precursor; Dried precursor is mixed with the mass ratio of sucrose by 9:1, and is immersed in pure water and carries out uniform wet mixed, after drying, obtain the iron manganese phosphate for lithium LiMn of even coated carbon source 0.5fe 0.5pO 4, then in the inert atmosphere stove of 600 DEG C constant temperature calcining 4h, finally obtain manganese phosphate lithium/carbon composite material LiMn 0.5fe 0.5pO 4/ C.The chemical property of resulting materials is 161.1mAh/g, and the conservation rate of 100 times of circulating under 0.5C multiplying power is 97.3%, and structure is olivine-type structure, and without dephasign peak, particle size is 3-8 μm, and wherein, carbon content is 2.51%.As Fig. 1, Fig. 2, Fig. 3, Fig. 4.
Comparative example 1
In beaker, add a certain amount of pure water, then add phosphoric acid, then add lithium hydroxide, wherein mol ratio is Li:P=3:1, and after 20min reacts completely, adding mass concentration is 6% lithium hydroxide solution, makes the pH value of mixed liquor reach 12.5; In mixed liquor, add manganese sulfate and ferrous sulfate again, mol ratio is Mn:Fe:P=0.5:0.5:1; Mixed liquor is gone in water heating kettle, by its constant temperature 12h at the temperature of 180 DEG C, after question response completes, reactor is taken out, open after at room temperature naturally cooling, after filtration, wash, and dry at 80 DEG C of temperature, be iron manganese phosphate for lithium LiMn 0.5fe 0.5pO 4precursor; Dried precursor is mixed with the mass ratio of sucrose by 9:1, and is immersed in pure water and carries out uniform wet mixed, after drying, obtain the iron manganese phosphate for lithium LiMn of even coated carbon source 0.5fe 0.5pO 4, then in the inert atmosphere stove of 600 DEG C constant temperature calcining 4h, finally obtain manganese phosphate lithium/carbon composite material LiMn 0.5fe 0.5pO 4/ C.The chemical property of resulting materials is 50.8mAh/g, and particle size is 30-40 μm, as Fig. 5.
Comparative example 2
By ethylene glycol with water by volume for 1:3 mixes, first in glycol water, add phosphoric acid, fully add lithium hydroxide again after mixing, wherein mol ratio is Li:P=3:1, after 40min reacts completely, adding mass concentration is 6% lithium hydroxide solution, makes the pH value of mixed liquor reach 12.5; In mixed liquor, add manganese sulfate and ferrous sulfate again, mol ratio is Mn:Fe:P=0.5:0.5:1; Mixed liquor is gone in water heating kettle, by its constant temperature 12h at the temperature of 180 DEG C, after having reacted, reactor is taken out, open after at room temperature naturally cooling, after filtration, wash, and dry at 80 DEG C of temperature, be iron manganese phosphate for lithium LiMn 0.5fe 0.5pO 4precursor; Dried precursor is mixed with the mass ratio of sucrose by 9:1, and is immersed in pure water and carries out uniform wet mixed, after drying, obtain the iron manganese phosphate for lithium LiMn of even coated carbon source 0.5fe 0.5pO 4, then in the inert atmosphere stove of 750 DEG C constant temperature calcining 2h, finally obtain manganese phosphate lithium/carbon composite material LiMn 0.5fe 0.5pO 4/ C.The chemical property of resulting materials is 80.7mAh/g, and particle size is 20-30 μm, as Fig. 6.
Embodiment 2
By polyethylene glycol (200) with water by volume for 1:2 mixes, first in polyethylene glycol (200) aqueous solution, add phosphoric acid, lithium hydroxide is added again after abundant mixing, wherein mol ratio is Li:P=3:1, after 30min reacts completely, adding mass concentration is 6% lithium hydroxide solution, makes the pH value of mixed liquor reach 11; In mixed liquor, add manganese sulfate and ferrous sulfate again, mol ratio is Mn:Fe:P=0.2:0.8:1; Mixed liquor is gone in water heating kettle, by its constant temperature 15h at the temperature of 180 DEG C, after having reacted, reactor is taken out, open after at room temperature naturally cooling, after filtration, wash, and dry at 80 DEG C of temperature, be iron manganese phosphate for lithium LiMn 0.8fe 0.2pO 4precursor; Dried precursor is mixed with the mass ratio of citric acid by 4:1, and is immersed in pure water and carries out uniform wet mixed, after drying, obtain the iron manganese phosphate for lithium LiMn of even coated carbon source 0.8fe 0.2pO 4, then in the inert atmosphere stove of 650 DEG C constant temperature calcining 3h, finally obtain manganese phosphate lithium/carbon composite material LiMn 0.8fe 0.2pO 4/ C.The chemical property of resulting materials is 138.6 mAh/g, and the conservation rate of 40 times of circulating under 0.5C multiplying power is 99.1%, and structure is olivine-type structure, and without dephasign peak, wherein, carbon content is 2.77%.
Embodiment 3
By polyethylene glycol (600) with water by volume for 1:1 mixes, first in polyethylene glycol (600) aqueous solution, add phosphoric acid, lithium hydroxide is added again after abundant mixing, wherein mol ratio is Li:P=3:1, after 45min reacts completely, adding mass concentration is 6% lithium hydroxide solution, makes the pH value of mixed liquor reach 13; In mixed liquor, add manganese sulfate and ferrous sulfate again, mol ratio is Mn:Fe:P=0.7:0.3:1; Mixed liquor is gone in water heating kettle, by its constant temperature 3h at the temperature of 200 DEG C, after having reacted, reactor is taken out, open after at room temperature naturally cooling, after filtration, wash, and dry at 80 DEG C of temperature, be iron manganese phosphate for lithium LiMn 0.7fe 0.3pO 4precursor; Dried precursor is mixed with the mass ratio of polyethylene glycol by 11:1, and is immersed in pure water and carries out uniform wet mixed, after drying, obtain the iron manganese phosphate for lithium LiMn of even coated carbon source 0.7fe 0.3pO 4, then in the inert atmosphere stove of 700 DEG C constant temperature calcining 5h, finally obtain manganese phosphate lithium/carbon composite material LiMn 0.7fe 0.3pO 4/ C.The chemical property of resulting materials is 111.9 mAh/g, and wherein, carbon content is 2.99%.
Embodiment 4
By polyethylene glycol (300) with water by volume for 1:8 mixes, first in polyethylene glycol (300) aqueous solution, add phosphoric acid, lithium hydroxide is added again after abundant mixing, wherein mol ratio is Li:P=3:1, after 30min reacts completely, adding mass concentration is 6% lithium hydroxide solution, makes the pH value of mixed liquor reach 11; In mixed liquor, add manganese chloride and frerrous chloride again, mol ratio is Mn:Fe:P=0.6:0.4:1; Mixed liquor is gone in water heating kettle, by its constant temperature 12h at the temperature of 180 DEG C, after having reacted, reactor is taken out, open after at room temperature naturally cooling, after filtration, wash, and dry at 80 DEG C of temperature, be iron manganese phosphate for lithium LiMn 0.6fe 0.4pO 4precursor; Dried precursor is mixed with the mass ratio of glucose by 5:1, and is immersed in pure water and carries out uniform wet mixed, after drying, obtain the iron manganese phosphate for lithium LiMn of even coated carbon source 0.6fe 0.4pO 4, then in the inert atmosphere stove of 550 DEG C constant temperature calcining 6h, finally obtain manganese phosphate lithium/carbon composite material LiMn 0.6fe 0.4pO 4/ C.The chemical property of resulting materials is 88.3mAh/g, and wherein, carbon content is 2.26%.

Claims (8)

1. the iron manganese phosphate for lithium that crystal formation is controlled or a preparation method for its composite material, is characterized in that comprising the following steps:
(1) polyethylene glycol is mixed with the volume ratio of water by 1:1-10, in Aqueous Solutions of Polyethylene Glycol, add phosphoric acid, fully add lithium hydroxide again, wherein mol ratio Li:P=3:1 after mixing, after question response is complete; Add lithium hydroxide solution, regulate ph value of mixture=11-13; Manganese source and ferrous source is added again, mol ratio Mn:Fe:P=x:(1-x in mixed liquor): 1, (0.5≤x < 1);
(2) step (1) gained mixed liquor is gone in water heating kettle, by water heating kettle constant temperature 3-15h at the temperature of 150-220 DEG C, reacted rear cooling, after filtration, wash and drying, be iron manganese phosphate for lithium LiMn xfe 1-xpO 4, 0.5≤x < 1;
(3) after precursor carbon step (2) obtained is coated in the inert atmosphere stove of 550-750 DEG C constant temperature 2-8h, finally obtain manganese phosphate lithium/carbon composite material LiMn xfe 1-xpO 4/ C.
2. preparation method according to claim 1, is characterized in that: the polyethylene glycol described in step (1) is one or two or more kinds in polyethylene glycol (200), polyethylene glycol (300), polyethylene glycol (400) and polyethylene glycol (600).
3. the iron manganese phosphate for lithium that a kind of crystal formation according to claim 1 is controlled and the preparation of composite material thereof, is characterized in that: step (1) lithium hydroxide solution mass concentration is 6%.
4. preparation method according to claim 1, is characterized in that: reacting completely described in step (1) refers to the temperature return room temperature of mixed liquor, and the reaction time is generally 15-50min.
5. preparation method according to claim 1, is characterized in that: described manganese source is selected from one in manganese chloride or manganese sulfate or two kinds; Ferrous source is selected from one in frerrous chloride or ferrous sulfate or two kinds.
6. preparation method according to claim 1, is characterized in that: step (3) described carbon source is one in sucrose, glucose, citric acid, polyethylene glycol or two kinds.
7. preparation method according to claim 1, is characterized in that: the mass ratio of the coated process of step (3) described carbon iron manganese phosphate for lithium used and carbon source is 4-12:1.
8. preparation method according to claim 1, is characterized in that: step (3) described manganese phosphate lithium/carbon composite material LiMn xfe 1-xpO 4carbon content in/C is 2.0-3.0wt%.
CN201410804443.6A 2014-12-19 2014-12-19 Preparation method of lithium manganese iron phosphate or lithium manganese iron phosphate composite material in controllable crystal form Pending CN104733709A (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105036103A (en) * 2015-08-03 2015-11-11 山东威能环保电源科技股份有限公司 Preparation method of cuboid lithium battery anode lithium ferric manganese phosphate material
CN107623117A (en) * 2017-10-10 2018-01-23 合肥国轩高科动力能源有限公司 A kind of preparation method of high power capacity, high-tap-density lithium iron phosphate material
CN107768613A (en) * 2017-09-01 2018-03-06 上海交通大学 A kind of preparation method of the iron manganese phosphate for lithium of carbon coated
CN112670475A (en) * 2020-12-23 2021-04-16 沁新集团(天津)新能源技术研究院有限公司 Lithium iron phosphate composite material, preparation method thereof, lithium battery using composite material and battery power vehicle
CN113078319A (en) * 2021-03-26 2021-07-06 天津斯科兰德科技有限公司 Preparation method of lithium iron manganese phosphate/carbon composite nanoparticle positive electrode material

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105036103A (en) * 2015-08-03 2015-11-11 山东威能环保电源科技股份有限公司 Preparation method of cuboid lithium battery anode lithium ferric manganese phosphate material
CN105036103B (en) * 2015-08-03 2017-08-01 山东威能环保电源科技股份有限公司 A kind of preparation method of cuboid-type anode material of lithium battery lithium ferric manganese phosphate
CN107768613A (en) * 2017-09-01 2018-03-06 上海交通大学 A kind of preparation method of the iron manganese phosphate for lithium of carbon coated
CN107623117A (en) * 2017-10-10 2018-01-23 合肥国轩高科动力能源有限公司 A kind of preparation method of high power capacity, high-tap-density lithium iron phosphate material
CN107623117B (en) * 2017-10-10 2020-12-11 合肥国轩高科动力能源有限公司 Preparation method of high-capacity and high-tap-density lithium iron phosphate material
CN112670475A (en) * 2020-12-23 2021-04-16 沁新集团(天津)新能源技术研究院有限公司 Lithium iron phosphate composite material, preparation method thereof, lithium battery using composite material and battery power vehicle
CN113078319A (en) * 2021-03-26 2021-07-06 天津斯科兰德科技有限公司 Preparation method of lithium iron manganese phosphate/carbon composite nanoparticle positive electrode material

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