CN107768613A - A kind of preparation method of the iron manganese phosphate for lithium of carbon coated - Google Patents
A kind of preparation method of the iron manganese phosphate for lithium of carbon coated Download PDFInfo
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Abstract
The present invention relates to a kind of preparation method of the iron manganese phosphate for lithium of carbon coated, comprise the following steps：(1) microcosmic salt, manganese salt, molysite, lithium salts and reducing agent are dissolved with water, and after be well mixed with organic solvent, progress solvent thermal reaction, obtains iron manganese phosphate for lithium nano material；(2) iron manganese phosphate for lithium nano material and carbon source are well mixed, high-temperature heat treatment is then carried out under gas shield, obtain the iron manganese phosphate for lithium of carbon coated.Compared with prior art, the iron manganese phosphate for lithium well-crystallized of carbon coated produced by the present invention, purity is high, particle diameter is small, outstanding chemical property, wherein LiMn are showed as anode material of lithium battery0.70Fe0.30PO4/ C-material charge/discharge capacity under 0.1C multiplying powers reaches 166mAh/g, and close to theoretical value 170mAh/g, and this method uses conventional phosphate, manganese salt and molysite raw material sources are wide and cost is cheap for raw material.
Description
Technical field
The invention belongs to technical field of lithium ion, and in particular to a kind of preparation side of the iron manganese phosphate for lithium of carbon coated
Method.
Background technology
Iron manganese phosphate lithium material (LiMn1-xFexPO4(0<x<1)) there is abundant raw material, cost is low, specific capacity is higher, to ring
Border is friendly, nontoxic, heat endurance is good etc. it is prominent the advantages of, be industrialization of new generation anode material for lithium-ion batteries it
One.The main preparation methods of iron manganese phosphate for lithium have high temperature solid-state method, sol-gal process, water/solvent-thermal method, spray drying heat at present
Solution, coprecipitation and polyol process etc..
High temperature solid-state method：Zhang Bin et al. (J.Power Sources, 2011,196,6992-6996) are sub- with oxalic acid
Iron, manganese oxalate, lithium carbonate and ammonium dihydrogen phosphate are raw material, and ball milling sinters to obtain iron manganese phosphate lithium material LiMnxFe1-xPO4/C(x
=0.7,0.8,0.9).Ding Bo et al. (ACS Appl.Mater.Interface, 2013,5,12120-12126) are with acetic acid
Lithium, ferrous oxalate, manganese acetate and ammonium dihydrogen phosphate and Super P ball milling in acetone, are dried, in 350 DEG C of pre-burnings, pre-burning production
Thing and sucrose ball milling again, then obtain iron manganese phosphate lithium material LiMn in 600 DEG C of high temperature sinterings1-xFexPO4/ C (x=0,
0.3)。
Sol-gel process can be such that reaction raw materials are mixed in the other contact of atom or molecular level, select suitable organic chelate
Mixture, is thermally formed colloidal sol and gel, and sintering obtains iron manganese phosphate lithium material.The shortcomings that method is that technological parameter is complicated, and energy
Consume larger.
Water/solvent-thermal method can control material morphology, and material crystalline is good, and lattice defect is few, and purity is high.The method exists
In closed reactor, synthesized under high-temperature and high-pressure conditions.
Pyrolysismethod is spray-dried using nitrogen or compressed air as carrier gas, mixed solution quick break and drying, can usually be obtained
The porous material larger to specific surface area.And coprecipitation is co-precipitated using metal salt and phosphate radical, then add lithium salts high temperature sintering
Material is obtained, the primary particle particle diameter of material is generally large.Polyol process：Mainly using reactant in polynary mixed alkoxide solution
Reaction obtains product into predecessor, then high temperature sintering in system.Using polyol process, the primary particle particle diameter one of synthetic product
As it is small and uniform.For example Han Xu et al. (RSC Adv., 2016,6,27164-27169) are by manganese acetate, ferrous sulfate aqueous solution
Mixing, diethylene glycol is added, 140 DEG C of heating stirrings 1 hour, instills lithium dihydrogen phosphate solution, 140 DEG C are continued stirring 4 hours, so
After cool down, centrifuge, add aqueous sucrose solution, dry, 680 DEG C of high temperature sinterings obtain iron manganese phosphate lithium material LiMnxFe1- xPO4/ C (x=0.2,0.5,0.8).
With respect to LiFePO 4 material, the electronic conductivity and ionic diffusion coefficient of lithium manganese phosphate are lower.Using commonsense method
The pure phosphoric acid manganese lithium activity of preparation is very low, and chemical property is poor.Change as a result, it is often necessary to carry out many-side to lithium manganese phosphate material
Property, to improve its chemical property.
The content of the invention
It is an object of the present invention to overcome the above-mentioned drawbacks of the prior art and provide a kind of phosphoric acid of carbon coated
The preparation method of ferromanganese lithium.
The purpose of the present invention can be achieved through the following technical solutions：
A kind of preparation method of the iron manganese phosphate for lithium of carbon coated, comprises the following steps：
(1) microcosmic salt, manganese salt, molysite, lithium salts and reducing agent are dissolved with water, and after be well mixed with organic solvent, progress is molten
Agent thermal response, obtain iron manganese phosphate for lithium nano material；
(2) iron manganese phosphate for lithium nano material and carbon source are well mixed, high-temperature heat treatment are then carried out under gas shield,
Obtain the iron manganese phosphate for lithium of carbon coated.
Preferably, described organic solvent is DMF, polyethylene glycol 400 or ethylene glycol.
The pioneering reaction system using " water+organic solvent " of the present invention, especially with " water+DMF "
Reaction system.The organic solvent of addition can increase the viscosity of reaction dissolvent, slow down the speed of ion diffusion and reaction, so as to
Limitation material crystals particle is grown up, and making the material granule morphology controllable of generation, in Nano grade (primary particle is approximately less than
200nm), and then help to lift its chemical property.
Preferably, the volume ratio of aqueous phase and organic solvent phase is 1 in solvent thermal reaction in step (1):2~1:1.
Aqueous phase and organic phase should keep suitable ratio, and excessive water can make it that the pattern particle of material is excessive, sometimes
Material granule is set to be more than 500nm or be micron diamond type；And organic solvent it is mutually excessive when, impurities phase, therefore this hair may be born
The volume ratio of aqueous phase and organic solvent phase is 1 in solvent thermal reaction in bright step (1):2~1:1.
Preferably, the temperature of described solvent thermal reaction is 150~200 DEG C, and the reaction time is 6~24h.
Preferably, described microcosmic salt is ammonium dihydrogen phosphate, and manganese salt is manganese sulfate, and molysite is ferrous sulfate, and lithium salts is hydrogen-oxygen
Change lithium, reducing agent is citric acid or ascorbic acid.
Preferably, in step (1), microcosmic salt, manganese salt, molysite, lithium salts and reducing agent are dissolved with water, and mix with organic solvent
Uniform method, using following steps：
Mixed after microcosmic salt, manganese salt and molysite are dissolved in into water respectively, add the aqueous solution of reducing agent or reducing agent, be well mixed
Afterwards, organic solvent is added, is eventually adding the aqueous solution of lithium source；
Or, mixed after microcosmic salt, manganese salt and molysite are dissolved in into water respectively, the aqueous solution of lithium source is added, after being well mixed, then is added
Enter organic solvent, be eventually adding the aqueous solution of reducing agent or reducing agent.
Preferably, the mol ratio of described microcosmic salt, transition metal salt and lithium salts is 1:1:3, transition metal salt is by institute
Manganese salt and the molysite composition stated.
Inorganic salts are first dissolved in water, are first that phosphate, manganese salt and molysite is good in aqueous dissolution, and with ionized form
In the presence of.It is that especially ferrous ion is easily oxidized in atmosphere in order to suppress iron ion and manganese ion oxidation to add reducing agent
Ferric ion, it is to disperse all kinds of ions to add organic solvent, is allowed to more uniformly spread, the product grain so obtained is big
It is small to be also more uniformly distributed.
Preferably, the chemical general formula for the iron manganese phosphate for lithium nano material that step (1) obtains is LiMn1-xFexPO4, wherein 0<x
<1。
It is further preferred that 0.2≤x≤0.3.In the span, not only make material granule pattern smaller and uniform；And
And cause material that there is higher energy density compared with high Mn content.
Preferably, described carbon source includes sucrose, glucose, carbonylation beta-schardinger dextrin or phenolic resin, iron manganese phosphate for lithium
The mass ratio of nano material and carbon source is 99:1~70:30.
Preferably, described carbon source includes sucrose, glucose or phenolic resin.
Preferably, iron manganese phosphate for lithium nano material and carbon source are spray-dried after being mixed by method, the liquid phase of high-energy ball milling
Method or heating stirring to the method being evaporated is well mixed in the liquid phase.
Preferably, the gas in step (2) is the mixed gas that inert gas and hydrogen form, hydrogen in mixed gas
Volume content is 2~10%.
Preferably, the temperature of step (2) high temperature heat treatment is 500~800 DEG C, and the time is 2~5h.
Compared with prior art, the invention has the advantages that：
The present invention uses ammonium dihydrogen phosphate, manganese sulfate, ferrous sulfate, lithium hydroxide to enter again after solvent-thermal process for raw material
Row high-temperature heat treatment, obtain the iron manganese phosphate for lithium (LiMn of the high-performance carbon coated of lithium ion battery1-xFexPO4/ C) series is just
Pole material, well-crystallized, purity is high, particle diameter is small, outstanding chemical property is showed as anode material of lithium battery.Wherein
LiMn0.70Fe0.30PO4/ C-material charge/discharge capacity under 0.1C multiplying powers reaches 166mAh/g, close to theoretical value 170mAh/g；
Discharge capacity under 1C and 5C multiplying powers is respectively up to 154mAh/g and 140mAh/g.And this method uses conventional phosphate, manganese
Salt and molysite are raw material, and raw material sources are wide and cost is cheap.
Brief description of the drawings
Fig. 1 is the XRD spectra of the iron manganese phosphate for lithium of the obtained carbon coated of embodiment 1；
Fig. 2 is the SEM figures of the obtained cladding iron manganese phosphate for lithium of embodiment 1；
When the LiFePO 4 for the carbon coated that Fig. 3 is prepared for embodiment 1 is as anode material for lithium-ion batteries, battery fills
Discharge curve；
Fig. 4 be the present invention carbon coated LiFePO 4 as anode material for lithium-ion batteries when, specific discharge capacity with
The curve of cycle-index.
Embodiment
The present invention is described in detail with specific embodiment below in conjunction with the accompanying drawings, but the present invention is not limited to following implementation
Example.
A kind of preparation method of the iron manganese phosphate for lithium of carbon coated, comprises the following steps：
(1) microcosmic salt, manganese salt, molysite, lithium salts and reducing agent are dissolved with water, and after be well mixed with organic solvent, progress is molten
Agent thermal response, obtain iron manganese phosphate for lithium nano material；
(2) iron manganese phosphate for lithium nano material and carbon source are well mixed, high-temperature heat treatment are then carried out under gas shield,
Obtain the iron manganese phosphate for lithium of carbon coated.
Embodiment 1
(1) manganese sulfate, ferrous sulfate, ammonium dihydrogen phosphate are weighed, is dissolved in water respectively, is mixed, adds ascorbic acid solution, is mixed
Close uniformly, add DMF, be eventually adding lithium hydroxide aqueous solution, wherein ammonium dihydrogen phosphate and lithium hydroxide
Mol ratio be 3:1, manganese sulfate is equal with the molal quantity of ammonium dihydrogen phosphate with the molal quantity sum of ferrous sulfate, manganese sulfate and sulphur
Sour ferrous molal quantity sum and the mol ratio of reducing agent (ascorbic acid) are 1:2,1-2 hours are stirred at room temperature, are transferred to polytetrafluoro
Ethylene reaction kettle, wherein solvent thermal reaction 12 hours at 180 DEG C, the volume ratio of aqueous phase and organic solvent phase are 3:5.After reaction from
The heart separates, and obtains iron manganese phosphate for lithium (LiMn1-xFexPO4(0<x<1)) nano material.
(2) iron manganese phosphate for lithium nano material and carbon source are weighed, carbon source can be sucrose or phenolic resin, and iron manganese phosphate for lithium is received
Rice material and the mass ratio of carbon source are 80:20, add a small amount of absolute ethyl alcohol, high-energy ball milling 6 hours (350rpm), drying, Ran Hou
In hydrogen-argon-mixed atmosphere (volume fraction of hydrogen be 5%), 550 DEG C of high temperature sinterings 4 hours, the iron manganese phosphate for lithium of carbon coating is obtained
Material.
Fig. 1 is the iron manganese phosphate lithium material LiMn of carbon coating0.70Fe0.30PO4/ C XRD spectrum (being carbon source from sucrose).
Its XRD and LiMnPO4Standard diagram (JSPDF 74-0375) peak type coincide, and free from admixture peak exist.Fig. 2 (a) and Fig. 2
(b) be respectively carbon coating iron manganese phosphate lithium material LiMn0.75Fe0.25PO4/ C and LiMn0.70Fe0.30PO4/ C SEM figures.From figure
It can be seen that two kinds of nano-grains are uniform in size, width about 50-80nm, length about 100-150nm.
Embodiment 2
Iron manganese phosphate for lithium (LiMn in the present embodiment1-xFexPO4(0<x<1)) preparation method of nano material and the phase of embodiment 1
Together, iron manganese phosphate for lithium nano material and glucose or carbonylation beta-schardinger dextrin are weighed, can also add graphene oxide or carbon nanometer
Pipe is dispersed in aqueous phase ultrasonic mixing, wherein, the mass ratio of iron manganese phosphate for lithium and glucose or carbonylation beta-schardinger dextrin is 80:20,
Powder is collected using spray drying process, then 550 DEG C of high temperature sinterings in hydrogen-argon-mixed atmosphere (volume fraction of hydrogen is 5%)
4 hours, obtain the iron manganese phosphate lithium material of carbon coating.
Embodiment 3
The present embodiment iron manganese phosphate for lithium (LiMn1-xFexPO4(0<x<1)) preparation method of nano material and embodiment 1 are basic
Identical, difference is, the organic solvent selection polyethylene glycol 400 in the present embodiment.
Embodiment 4
(1) manganese sulfate, ferrous sulfate, ammonium dihydrogen phosphate are weighed, is dissolved in water respectively, is mixed, adds lithium hydroxide solution, is mixed
Close uniform, add ethylene glycol, monohydrate potassium is finally directly added into dissolving, wherein ammonium dihydrogen phosphate and lithium hydroxide
Mol ratio is 3:1, manganese sulfate is equal with the molal quantity of ammonium dihydrogen phosphate with the molal quantity sum of ferrous sulfate, manganese sulfate and sulfuric acid
Ferrous molal quantity sum and the mol ratio of reducing agent (citric acid) are 2:1,1-2 hours are stirred at room temperature, are transferred to polytetrafluoroethylene (PTFE)
Reactor, wherein solvent thermal reaction 15 hours at 180 DEG C, the volume ratio of aqueous phase and organic solvent phase are 1:1.Centrifugation point after reaction
From obtaining iron manganese phosphate for lithium (LiMn1-xFexPO4(0<x<1)) nano material.
(2) iron manganese phosphate for lithium nano material and carbon source are weighed, carbon source can be sucrose or phenolic resin, and iron manganese phosphate for lithium is received
Rice material and the mass ratio of carbon source are 80:20, add a small amount of absolute ethyl alcohol, high-energy ball milling 6 hours (350rpm), drying, Ran Hou
In hydrogen-argon-mixed atmosphere (volume fraction of hydrogen be 5%), 550 DEG C of high temperature sinterings 4 hours, the iron manganese phosphate for lithium of carbon coating is obtained
Material.
Embodiment 5
The iron manganese phosphate for lithium of carbon coated prepared by embodiment 1 and conductive agent Super P, polyfluortetraethylene of binding element is molten
Liquid (solute is PVDF 760, and solvent is 1-METHYLPYRROLIDONE) is well mixed, stirs into slurry, the iron manganese phosphate for lithium of carbon coated,
Super P, the mass ratio of PVDF 760 are 80:10:10, slurry is scratched on aluminium foil, positive pole of cutting into slices to obtain.Metal lithium sheet is negative
Pole, electrolyte are that (solvent is ethylene carbonate and dimethyl carbonate mixed solution to 1mol/L lithium hexafluorophosphate solutions, and volume ratio is
1:1), single layered porous polyethylene film is barrier film, is assembled into lithium battery, carries out charge-discharge test using 0.1C electric currents, obtains carbon bag
The lithium iron manganese phosphate anode material LiMn covered0.70Fe0.30PO4/ C charging and discharging curve, as shown in Figure 3.Initial charge specific capacity is
187mAh/g, specific discharge capacity 166mAh/g, close to the theoretical specific capacity 170mAh/g of the positive electrode of lithium manganese phosphate.
LiMn0.70Fe0.30PO4Specific discharge capacities of/the C under 1C and 5C multiplying powers is respectively 154mAh/g, 140mAh/g, 100 circulations
Afterwards, capacity can keep 95% and 88% respectively；Adjust Mn and Fe ratio, the LiMn being prepared0.75Fe0.25PO4/ C is in 1C
It is respectively 142mAh/g and 121mAh/g with the specific discharge capacity under 5C multiplying powers, capability retention is the same, as shown in Figure 4.
Embodiment 6
The present embodiment is substantially the same manner as Example 1, and difference is, in the present embodiment, solvent thermal reaction in step (1)
The volume ratio of middle aqueous phase and organic solvent phase is 1:2.
Embodiment 7
The present embodiment is substantially the same manner as Example 1, and difference is, in the present embodiment, by adjusting manganese sulfate and sulphur
Sour ferrous ratio so that final obtained iron manganese phosphate for lithium (LiMn1-xFexPO4(0<x<1)) chemical formula of nano material is
LiMn0.99Fe0.01PO4。
Embodiment 8
The present embodiment is substantially the same manner as Example 1, and difference is, in the present embodiment, by adjusting manganese sulfate and sulphur
Sour ferrous ratio so that final obtained iron manganese phosphate for lithium (LiMn1-xFexPO4(0<x<1)) chemical formula of nano material is
LiMn0.01Fe0.99PO4。
Embodiment 9
The present embodiment is substantially the same manner as Example 1, and difference is, in the present embodiment, the heat treatment of step (2) high temperature
Temperature be 500 DEG C, time 5h.
Embodiment 10
The present embodiment is substantially the same manner as Example 1, and difference is, in the present embodiment, the heat treatment of step (2) high temperature
Temperature be 800 DEG C, time 2h.
Embodiment 11
The present embodiment is substantially the same manner as Example 1, and difference is, in the present embodiment, iron manganese phosphate for lithium in step (2)
The mass ratio of nano material and carbon source is 99:1.
Embodiment 12
The present embodiment is substantially the same manner as Example 1, and difference is, in the present embodiment, iron manganese phosphate for lithium in step (2)
The mass ratio of nano material and carbon source is 70:30.
Embodiment 13
The present embodiment is substantially the same manner as Example 1, and difference is, in the present embodiment, the temperature of solvent thermal reaction is
150 DEG C, reaction time 24h.
Embodiment 14
The present embodiment is substantially the same manner as Example 1, and difference is, in the present embodiment, the temperature of solvent thermal reaction is
200 DEG C, reaction time 6h.
Claims (10)
1. a kind of preparation method of the iron manganese phosphate for lithium of carbon coated, it is characterised in that comprise the following steps：
(1) microcosmic salt, manganese salt, molysite, lithium salts and reducing agent are dissolved with water, and after be well mixed with organic solvent, progress solvent heat
Reaction, obtains iron manganese phosphate for lithium nano material；
(2) iron manganese phosphate for lithium nano material and carbon source are well mixed, high-temperature heat treatment is then carried out under gas shield, is obtained
The iron manganese phosphate for lithium of carbon coated.
2. the preparation method of the iron manganese phosphate for lithium of a kind of carbon coated according to claim 1, it is characterised in that described has
Solvent is N,N-dimethylformamide, polyethylene glycol 400 or ethylene glycol.
A kind of 3. preparation method of the iron manganese phosphate for lithium of carbon coated according to claim 1 or 2, it is characterised in that step
(1) volume ratio of aqueous phase and organic solvent phase is 1 in solvent thermal reaction in:2~1:1.
4. the preparation method of the iron manganese phosphate for lithium of a kind of carbon coated according to claim 1, it is characterised in that described is molten
The temperature of agent thermal response is 150~200 DEG C, and the reaction time is 6~24h.
A kind of 5. preparation method of the iron manganese phosphate for lithium of carbon coated according to claim 1, it is characterised in that described phosphorus
Salt is ammonium dihydrogen phosphate, and manganese salt is manganese sulfate, and molysite is ferrous sulfate, and lithium salts is lithium hydroxide, and reducing agent is citric acid or resisted
Bad hematic acid.
A kind of 6. preparation method of the iron manganese phosphate for lithium of carbon coated according to claim 1, it is characterised in that step (1)
In, microcosmic salt, manganese salt, molysite, lithium salts and reducing agent, and the method being well mixed with organic solvent are dissolved with water, using following step
Suddenly：
Mixed after microcosmic salt, manganese salt and molysite are dissolved in into water respectively, add the aqueous solution of reducing agent or reducing agent, after being well mixed,
Organic solvent is added, is eventually adding the aqueous solution of lithium source；
Or, mixed after microcosmic salt, manganese salt and molysite are dissolved in into water respectively, the aqueous solution of lithium source is added, after being well mixed, has been added
Solvent, it is eventually adding the aqueous solution of reducing agent or reducing agent.
A kind of 7. preparation method of the iron manganese phosphate for lithium of carbon coated according to claim 1,5 or 6, it is characterised in that institute
The mol ratio of microcosmic salt, transition metal salt and the lithium salts stated is 1:1:3, transition metal salt is by described manganese salt and molysite group
Into.
A kind of 8. preparation method of the iron manganese phosphate for lithium of carbon coated according to claim 1, it is characterised in that described carbon
Source includes sucrose, glucose, beta-schardinger dextrin or phenolic resin is carbonylated, and the mass ratio of iron manganese phosphate for lithium nano material and carbon source is
99:1~70:30.
A kind of 9. preparation method of the iron manganese phosphate for lithium of carbon coated according to claim 1, it is characterised in that step (2)
In the mixed gas that is formed for inert gas and hydrogen of gas, the volume content of hydrogen is 2~10% in mixed gas.
A kind of 10. preparation method of the iron manganese phosphate for lithium of carbon coated according to claim 1, it is characterised in that step (2)
The temperature of high temperature heat treatment is 500~800 DEG C, and the time is 2~5h.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109244391A (en) * | 2018-08-22 | 2019-01-18 | 江苏元景锂粉工业有限公司 | A kind of nitrogen mixes carbon coating iron manganese phosphate lithium material and preparation method thereof |
| CN112125292A (en) * | 2020-08-14 | 2020-12-25 | 中国科学院金属研究所 | Hydrothermal synthesis method of lithium manganese iron phosphate |
| CN114023953A (en) * | 2021-11-03 | 2022-02-08 | 惠州亿纬锂能股份有限公司 | Modified lithium iron manganese phosphate cathode material and preparation method and application thereof |
| CN114249310A (en) * | 2020-09-21 | 2022-03-29 | 中南大学 | Lithium ion battery composite positive electrode material LiMn1-xFexPO4Method for synthesizing/C |
| CN114899394A (en) * | 2022-06-29 | 2022-08-12 | 蜂巢能源科技股份有限公司 | Modified lithium iron manganese phosphate cathode material and preparation method and application thereof |
| CN114988386A (en) * | 2022-06-16 | 2022-09-02 | 蜂巢能源科技股份有限公司 | Lithium iron manganese phosphate positive electrode material and preparation method and application thereof |
| CN115818609A (en) * | 2022-11-24 | 2023-03-21 | 天津市捷威动力工业有限公司 | Lithium iron manganese phosphate material, preparation method thereof and battery |
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| CN109244391A (en) * | 2018-08-22 | 2019-01-18 | 江苏元景锂粉工业有限公司 | A kind of nitrogen mixes carbon coating iron manganese phosphate lithium material and preparation method thereof |
| CN109244391B (en) * | 2018-08-22 | 2021-06-22 | 江苏元景锂粉工业有限公司 | Nitrogen-doped carbon-coated lithium manganese iron phosphate material and preparation method thereof |
| CN112125292A (en) * | 2020-08-14 | 2020-12-25 | 中国科学院金属研究所 | Hydrothermal synthesis method of lithium manganese iron phosphate |
| CN114249310A (en) * | 2020-09-21 | 2022-03-29 | 中南大学 | Lithium ion battery composite positive electrode material LiMn1-xFexPO4Method for synthesizing/C |
| CN114023953A (en) * | 2021-11-03 | 2022-02-08 | 惠州亿纬锂能股份有限公司 | Modified lithium iron manganese phosphate cathode material and preparation method and application thereof |
| CN114988386A (en) * | 2022-06-16 | 2022-09-02 | 蜂巢能源科技股份有限公司 | Lithium iron manganese phosphate positive electrode material and preparation method and application thereof |
| CN114988386B (en) * | 2022-06-16 | 2024-02-02 | 蜂巢能源科技股份有限公司 | Lithium iron manganese phosphate positive electrode material, and preparation method and application thereof |
| CN114899394A (en) * | 2022-06-29 | 2022-08-12 | 蜂巢能源科技股份有限公司 | Modified lithium iron manganese phosphate cathode material and preparation method and application thereof |
| CN114899394B (en) * | 2022-06-29 | 2023-12-19 | 蜂巢能源科技股份有限公司 | Modified lithium iron manganese phosphate positive electrode material and preparation method and application thereof |
| CN115818609A (en) * | 2022-11-24 | 2023-03-21 | 天津市捷威动力工业有限公司 | Lithium iron manganese phosphate material, preparation method thereof and battery |
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