CN105355885A - Synthesis method of lithium ion battery composite cathode material LiMn1-xFexPO4/C - Google Patents

Synthesis method of lithium ion battery composite cathode material LiMn1-xFexPO4/C Download PDF

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CN105355885A
CN105355885A CN201510847231.0A CN201510847231A CN105355885A CN 105355885 A CN105355885 A CN 105355885A CN 201510847231 A CN201510847231 A CN 201510847231A CN 105355885 A CN105355885 A CN 105355885A
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carbon
lithium
carbon source
lithium ion
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胡国荣
曹雁冰
彭忠东
杜柯
程守强
陈鹏伟
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Central South University
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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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1397—Processes of manufacture of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • 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
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • 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 relates to a synthesis method of lithium ion battery composite cathode material LiMn1-xFexPO4/C. A manganese source, an iron source, a phosphorus source and an organic carbon source are evenly mixed and processed by a high-energy ball mill. Mixtures are subjected to heat treatment at 500-700 DEG C under the protection of inert atmosphere so that (Mn1-xFex)2P2O7/C can be prepared; then, pyrophosphate/carbon, a lithium source and a carbon source are mixed, heat treatment is performed at 600-750 DEG C under protection of inert atmosphere, and ferromanganese lithium phosphate/carbon anode materials with a composite conductive network are obtained. The synthesis method is suitable for large-scale industrialized production, the prepared materials are composed of secondary particles of primary nano-crystals covered with amorphous carbon, distribution is uniform, and the uniform conductive network is formed on the surfaces of phosphate particles in an in-situ mode. The obtained composite cathode material has high rate capacity and high compaction intensity and has good application prospects in the aspect of high-energy-density lithium ion batteries.

Description

A kind of lithium ion battery composite cathode material LiMn 1-xfe xpO 4the synthetic method of/C
Technical field
The invention belongs to technical field of lithium ion battery positive pole material preparation, relate to a kind of lithium ion battery with high energy density composite positive pole LiMn 1-xfe xpO 4the synthetic method of/C.
Background technology
Research and development has the positive electrode of high security, cheap green, high-energy-density, has important researching value and meaning to the research and development of energy storage (power) lithium ion battery.Polyanionic LiMnPO 4advantages such as positive electrode is good with high-voltage discharge platform, fail safe, aboundresources and become very potential anode material for lithium-ion batteries.LiMnPO 4there is higher voltage platform (4.1VvsLi +/ Li), LiMnPO 4compare LiFePO 4there is higher theoretical energy density.And LiMnPO 4energy density be considered to be in the lower maximum energy-density that can reach of electrochemical stability window of carbonate group electrolyte.But pure phase LiMnPO 4conductivity compares LiFePO 4poorer, belong to insulator.Simultaneously lithium ion diffusion is also limited one dimension passage, makes the migration rate of lithium ion under room temperature less.Therefore, LiMnPO can be utilized 4high potential make up LiFePO 4shortcoming, replace manganese element by part iron and form solid-solution material, make the conductivity of material obtain improvement to a certain extent, obtain the LiMn with applications well prospect 1-xfe xpO 4positive electrode.
Current coated modified carbon technique improves the most practical and effective means of phosphate-based chemical property.HPL company of Switzerland has issued one and has prepared LiMnPO 4the method (UK2007/093856) of/C material, the method obtains LiMnPO based on the sol-gel process of organic salt system 4material, obtains LiMnPO after high-energy ball milling mixes with conduction charcoal 4/ C material, the specific discharge capacity of the composite material adding 20% acetylene black under 1C and 5C multiplying power is respectively at 120mAh/g and more than 80mAh/g.But sol-gal process suitability for industrialized production difficulty is comparatively large, synthesis cycle is longer.And the carbon method of modifying mostly adopted is by the LiMnPO after crystallization 4material mixes with conductive carbon ball milling.Common carbon is coated only can form electron diffusion path in single surface of active material, can not provide continuous print electric transmission network.In order to reach considerable conductivity, often introduce more conductive carbon (20 ~ 40wt%), this will have a strong impact on volume energy density and the processing paintability of material, weakens LiMnPO 4the advantage of material itself.Meanwhile, people generally adopt the LiMnPO of the synthesis nanos such as sol-gal process, hydro thermal method, spray pyrolysis 4realize modification approach.The nanoscale LiMnPO of usual synthesis 4material is in battery charging and discharging carries out, and nano particle is easily reunited, and internal particle may lose electrical contact, causes the advantage on dynamics, cyclical stability not obvious.[KaoruDokko, TakeshiHachida, the MasayoshiWatanabe.LiMnPO such as Dokko 4nanoparticlesPreparedthroughtheReactionbetweenLi 3pO 4andMoltenAqua-complexofMnSO 4[J] .JElectrochemSoc, 2011158 (12): A1275-A1281] with Li 3pO 4with MnSO 4nH 2o is that raw material has synthesized nanometer LiMnPO by hydro thermal method at 190 DEG C 4, be then that carbon source carries out coated process with glucose.The specific discharge capacity of 0.01C is 135mAhg -1, but comparatively under high magnification 1C specific discharge capacity be only 83mAhg -1, only refer to the performance of circulation 5 times in literary composition, show bad.
Summary of the invention
For phosphate material Problems existing in chemical property and material, bond material micro-nano of the present invention and the coated modification approach of carbon, preparation has the micro-nano compound structure of continuous conduction network, namely with the coated reactive nanoparticles of carbon for core is formed the structural system of overall dimension at micron order or submicron order, higher bulk density and short lithium ion the evolving path can be provided, improve energy density and high rate performance.Ensure that LiMn simultaneously 1-xfe xpO 4stablizing in/C forming process, ensures LiMn 1-xfe xpO 4the consistency of/C product.
For achieving the above object, technical scheme of the present invention is, lithium ion battery composite cathode material LiMn of the present invention 1-xfe xpO 4/ C, 0.1≤x≤0.7,1%≤carbon accounts for mass content≤5% in composite material, and preparation comprises the following steps:
1) Fe source, P source, Mn source and organic carbon source to be blended in ball-milling medium after dry method high-energy ball milling in the ratio of the molecular formula of required synthesis positive electrode, obtain presoma compound, wherein mol ratio Mn+Fe:P=1:1, the addition of organic carbon source accounts for target product content 1 ~ 10wt%;
2) by presoma compound under inert atmosphere protection through 500-700 DEG C of heat treatment, produce presoma (Mn 1-xfe x) 2p 2o 7/ C;
3) by step 2) presoma (Mn that obtains 1-xfe x) 2p 2o 7after/C material disintegrating, with lithium source, carbon source after high speed batch mixing merges, sinter under 600 DEG C ~ 750 DEG C conditions under inert atmosphere conditions, obtain LiMn 1-xfe xpO 4/ C composite positive pole; Mol ratio Mn+Fe:Li=1:1, the addition of carbon source accounts for target product content 1 ~ 15wt%; The rotating speed that its high speed batch mixing merges is not less than 600r/min.
In the present invention, described manganese source is preferably the one of manganese monoxide, manganese dioxide, mangano-manganic oxide.Described source of iron is preferably the middle one of di-iron trioxide, tri-iron tetroxide, or mixing ferrimanganic source is ferrous oxalate manganese, MnFe 2o 4in one.Described lithium source is preferably at least one of lithium hydroxide, lithium carbonate.Described phosphorus source is preferably at least one of ammonium phosphate, MAP, Diammonium phosphate (DAP), APP.
Step 3 of the present invention) in carbon source comprise organic carbon source, inorganic carbon source.Wherein step 1), 3) organic carbon source is preferably polysaccharide and macromolecule carbon source, the one particularly preferably in starch, polyvinyl alcohol, polypropylene, phenolic resins, polystyrene, polyacrylonitrile, polyvinylpyrrolidone.Step 3) in inorganic carbon source be one in superconduction carbon, conductive carbon fibre, carbon nano-tube.
Step 1 of the present invention), 3) in the hybrid mode of each composition be dry method.One in the first time dry method ball mill such as V-type ball mill used in combination, anistree ball mill, vibration at high speed ball mill.Wherein, preferred rotating speed is 100-400r/min.Pyrophosphate composite precursor i.e. (Mn 1-xfe x) 2p 2o 7the grinding mode of/C is the one in air-flow crushing, mechanical crushing.Second time batch mixing adopts the one in high speed mixer, fusion machine.Its medium speed is 600-1500r/min.Step 3) high speed batch mixing fusion preferably 3 ~ 6h.
Described protective atmosphere is the one of argon gas, nitrogen.
The present invention is preferred: step 1) in 2 ~ 4h of high-energy ball milling.Step 2) middle heat treatment 4 ~ 8h; Step 3) in sintering 2 ~ 8 hours.
The material that method of the present invention obtains has the composite material of micro--Na dual structure, is the secondary micron particles being obtained almost spherical by nano particle fusion growth.
Positive electrode test process of the present invention is: material is made into CR2025 type button cell and carries out charge and discharge cycles test.Coating method is adopted to prepare electrode, with METHYLPYRROLIDONE (NMP) for solvent, 8:1:1 takes active material, acetylene black and PVDF respectively in mass ratio, after mixing, be coated on pretreated aluminium foil, put into vacuum drying chamber and obtain positive plate 120 DEG C of dryings.In the glove box being full of argon gas, take metal lithium sheet as negative pole, 1molL -1liPF 6being dissolved in ethylene carbonate (EC)+dimethyl carbonate (DMC)+ethyl methyl carbonate (EMC) (volume ratio is 1:1:1) is electrolyte, Celgard2400 porous polypropylene film is barrier film, be assembled into button cell, Land electrochemical instrument carries out electro-chemical test.
The present invention is by two step dry mixed-synthesis in solid state, and the coated synergy of twice carbon prepares the dual structure of coexistent nano-micrometer grade particles; Construct three dimensional micron level carbon net grain structure in the material, make to be interconnected between nano active particle, form the conductive network be evenly distributed.Between particle, micron-sized carbon net can provide the duplicate transmissions passage of lithium ion and electronics, while the polarization of minimizing material and the internal resistance of cell, improve its tap density and processing characteristics.In preparation process of the present invention, the more important thing is and obtain (Mn by first step high-temperature dry mixing-solid phase reaction 1-xfe x) 2p 2o 7/ C precursor nanoparticle; The basis of this presoma further add lithium salts and carry out secondary carbon coated, by the coated micron particles making nano particle fusion growth obtain almost spherical of secondary mixed at high speed-carbon, successfully realize finally by sintering and prepare the positive electrode of the dual structure of coexistent nano-micrometer grade particles.This presoma of the present invention allows Mn and Fe fully spread by pre-synthesis, forms homogeneous phase phosphate solid solution, ensure that the distribution of Mn, Fe, P component on atomic level, and be beneficial to the carrying out of the embedding lithium of second step high temperature; In addition, in the adition process of raw material, inventor makes the mol ratio of (Mn+Fe) metal and P element be 1:1, with LiMPO 4middle component proportion is consistent, the chemical valence of Mn, Fe and P and LiMn 1-xfe xpO 4element valence corresponding in/C is identical, thus is beneficial to guarantee product LiMn 1-xfe xpO 4the uniformity of/C-structure; Moreover the carbon that inventor is decomposed by first time organic carbon source is coated, can realize the original position of pyrophosphate presoma evenly coated, is beneficial to and obtains the tiny nano-scale particle of primary particle, by the follow-up synthesis of the coated minimizing of carbon first LiMPO 4in carbon source addition.Next, inventor can carry out micronized modification to pyrophosphate granular precursor while pyrophosphate presoma and lithium source being carried out being dry mixed, namely in heat treatment embedding lithium process, realize second time carbon coated, obtain near spherical micron particles material (the i.e. secondary micron particles) LiMn be made up of multiple nano particles that amorphous carbon is coated 1-xfe xpO 4/ C (specifically can see Fig. 2 c).By twice coated distribution optimizing phosphate surface in-situ nano carbon network of uniform carbon, chemical property and the processing characteristics of positive electrode can be ensured under lower carbon content.
The present invention is by two step dry mixed-synthesis in solid state, and the coated synergy of twice carbon can reduce the addition of organic carbon source, forms LiMn at the embedding lithium of high temperature 1-xfe xpO 4in/C process, furnace atmosphere is more simple; Compared with the syntheti c route being raw material with oxalic acid ferromanganese, manganese carbonate and manganese acetate etc., the present invention adopts lithium carbonate and (Mn 1-xfe x) 2p 2o 7/ C is that the route of synthesis of raw material has minimum burn tinctuer, productive rate >85%, the carbon dioxide only having lithium carbonate to decompose in stove in after baking process and a small amount of carbon source are decomposed, thus furnace atmosphere can be made more simple, be beneficial to and realize the coated equal control of carbon, ensure the consistency of product.Make a nano particle further growth merge the micron particles obtaining almost spherical by secondary mixed at high speed-carbon is coated simultaneously, complete the structure of micro-nano composite material, form coexistent nano-micrometer grade particles dual structure and can have good processing characteristics in battery pole piece manufacture process, ensured that active material contacts with binding agent and the effective of conductive additive.To be electrolyte provide passage to the diffusion of electrode interior and transmission for the duct of nano-micrometer grade particles inside; And intragranular nano particle makes Li +greatly shorten in the diffusion length of material internal, its surface coated electrical-conductive nanometer carbon-coating just introduces electric transmission network in the inside of micrometer level porous particle, the high-effective conductive network formed realizes the fast transport of ion and electronics on nanoscale simultaneously, improves high rate performance.
The present invention adopts high temperature solid-state reducing process pre-synthesis (Mn in building-up process 1-xfe x) 2p 2o 7/ C presoma, decreases the dependence to Mn, Fe raw material, avoids the use of dispersion solvent, and efficient cost is low, is beneficial to large-scale industrial and produces.It is high that material prepared by the method has purity, and the coated uniformity of carbon is high, pattern rule, good physical properties, the feature that circulation performance is good.
Accompanying drawing explanation
Fig. 1 is the x-ray diffraction pattern of sample.(a, embodiment 1 product; B, embodiment 3 first step heat treatment pyrophosphate presoma).
Fig. 2 is LiMn 1-xfe xpO 4/ C composite shape appearance figure.(a, the SEM figure of embodiment 1 product; B, the high multiple TEM of embodiment 1 product schemes, c, the TEM of embodiment 3 product).
Fig. 3 is discharge curve under the different multiplying of product composition battery in embodiment 1.
Fig. 4 is product charging and discharging curve figure under 0.1C multiplying power in embodiment 2.
Fig. 5 is product charging and discharging curve figure under different multiplying in embodiment 3.
Fig. 6 is product charging and discharging curve figure under different multiplying in embodiment 4.
Fig. 7 is product cycle performance figure under 1C multiplying power in embodiment 3,4.
Embodiment
Following examples are intended to the present invention is described, instead of limitation of the invention further.
Embodiment 1
Mangano-manganic oxide, tri-iron tetroxide and ammonium dihydrogen phosphate are taken according to Mn:Fe:P mol ratio 0.8:0.2:1, and adds the polyvinyl alcohol of product material 5wt%, mix through anistree ball milling 4h, rotating speed 100r/min.By compound 600 ° of reaction 5h under argon gas atmosphere protection, obtain gray product.Then the grey pyrophosphate after mechanical crushing, lithium carbonate are mixed with superconduction carbon ratio example, wherein Li:P mol ratio 1:1 takes lithium carbonate, and superconduction carbon addition is the 1.5wt% of product.Be placed in high speed fusion machine mixing 3h, rotating speed 700r/min.Then under argon shield, 650 DEG C of calcining 8h are cooled to room temperature and obtain LiMn 0.8fe 0.2pO 4/ C composite positive pole (XRD figure is shown in embodiment Fig. 1 a, and shape appearance figure is shown in embodiment Fig. 2 a, 2b).As can be seen from shape appearance figure, two sub-micron grade spherical particles are constituted by a nano particle, growth in situ amorphous carbon layer between the nanoparticle surface and crystal grain, define continuous print conductive network, detect carbon containing 3.29wt% in this composite positive pole, under 0.1C, discharge capacity is 150.5mAh/g, 1C discharge capacity 138mAh/g first.
Embodiment 2
By Manganese Ferrite (MnFe 2o 4), diammonium hydrogen phosphate is according to (Mn+Fe): P mol ratio 1:1 takes, and adds the polypropylene of product 3wt%, and mixing is dispersed in the ball grinder of planetary ball mill, through planetary ball mill ball milling 2h, rotating speed 400r/min, obtains presoma compound.By compound 650 ° of reaction 8h under argon gas atmosphere protection, obtain (Mn 1/3fe 2/3) 2p 2o 7/ C pyrophosphate predecessor.Then pyrophosphate predecessor, lithium hydroxide are mixed with sucrose ratio, wherein Li:P mol ratio 1:1 takes lithium hydroxide, and sucrose addition is the 7wt% of product.Be placed in high-speed mixer mixing 5h, rotating speed 1000r/min.Then under argon shield, 750 DEG C of calcining 6h are cooled to room temperature and obtain LiMn 1/3fe 2/3pO 4/ C composite positive pole.Detect carbon containing 2.18wt% in this composite positive pole, at 0.1C discharge capacity 157.2mAh/g.
Embodiment 3
Ammonium phosphate, manganese dioxide, di-iron trioxide are taken according to Mn:Fe:P mol ratio 0.9:0.1:1, and adds the phenolic resins of product material 9wt%, mix through V-type batch mixing ball milling 3h, rotating speed 200r/min.By compound 550 ° of reaction 6h under argon gas atmosphere protection, obtain grey (Mn 0.9fe 0.1) 2p 2o 7/ C, detects XRD structure and sees embodiment Fig. 1 b.Then grey pyrophosphate, lithium carbonate are mixed with polypropylene ratio, wherein Li:P mol ratio 1:1 takes lithium carbonate, and polypropylene addition is the 15wt% of product.Be placed in high speed mixer mixing 6h, rotating speed 700r/min.Then under argon shield, 600 DEG C of calcining 4h are cooled to room temperature and obtain LiMn 0.9fe 0.1pO 4/ C composite positive pole (shape appearance figure is shown in embodiment Fig. 2 c).SEM shows amorphous carbon dispersion and forms conductive network between particles, and detect carbon containing 4.7wt% in this composite positive pole, under 0.1C, discharge capacity is 141.7mAh/g, 1C discharge capacity 125.1mAh/g first, circulates and keeps 94% in 250 weeks.
Embodiment 4
By ammonium dihydrogen phosphate, ferrous oxalate manganese Fe 0.5mn 0.5(C 2o 4) 2H 2o takes according to mol ratio 1:1, and adds the polystyrene of mixed material 2wt%, and dispersion is blended in anistree tiltedly bastard grinding machine 2.5h, rotating speed 120r/min, obtains precursor mixture.By compound 500 ° of reaction 4h under argon gas atmosphere protection, obtain grey (Mn 0.5fe 0.5) 2p 2o 7/ C.Then grey pyrophosphate, lithium hydroxide are mixed with starch proportion, wherein Li:P mol ratio 1:1 takes lithium carbonate, and starch addition is the 8wt% of product.Be placed in fusion machine mixing 4h, rotating speed 900r/min.Then under argon shield, 700 DEG C of calcining 8h are cooled to room temperature and obtain LiMn 0.5fe 0.5pO 4/ C composite positive pole.Detect carbon containing 1.6wt% in this composite positive pole, under 0.2C, discharge capacity is 156.5mAh/g, 1C discharge capacity 141.3mAh/g first, circulates and keeps 98% in 250 weeks.

Claims (10)

1. a lithium ion battery composite cathode material LiMn 1-xfe xpO 4the synthetic method of/C, is characterized in that, 0.1≤x≤0.7, and 1%≤carbon accounts for mass content≤5% in composite material, comprises the following steps:
1) Fe source, P source, Mn source and organic carbon source to be blended in ball-milling medium after dry method high-energy ball milling in the ratio of the molecular formula of required synthesis positive electrode, obtain presoma compound, wherein mol ratio Mn+Fe:P=1:1, the addition of organic carbon source accounts for target product content 1 ~ 10wt%;
2) by presoma compound under inert atmosphere protection through 500-700 DEG C of heat treatment, produce presoma (Mn 1-xfe x) 2p 2o 7/ C;
3) by step 2) presoma (Mn that obtains 1-xfe x) 2p 2o 7after/C material disintegrating, with lithium source, carbon source after high speed batch mixing merges, sinter under 600 DEG C ~ 750 DEG C conditions under inert atmosphere conditions, obtain LiMn 1-xfe xpO 4/ C composite positive pole; Mol ratio Mn+Fe:Li=1:1, the addition of carbon source accounts for target product content 1 ~ 15wt%; The rotating speed that its high speed batch mixing merges is not less than 600r/min.
2. method according to claim 1, is characterized in that: step 1) in the rotating speed of high-energy ball milling be 100-400r/min.
3. method according to claim 1 and 2, is characterized in that: step 1) in 2 ~ 4h of high-energy ball milling.
4. method according to claim 1, is characterized in that: step 3) high speed batch mixing merge rotating speed be 600-1500r/min.
5. the method according to claim 1 or 4, is characterized in that: step 3) high speed batch mixing fusion 3 ~ 6h.
6. method according to claim 1, is characterized in that: step 2) middle heat treatment 4 ~ 8h; Step 3) in sintering 2 ~ 8 hours.
7. the method according to claim 1 or 2 or 4 or 6, is characterized in that: step 1) in, the one that what ball milling adopted is in V-type ball mill, tiltedly bastard grinding machine, planetary ball mill; The grinding mode of pyrophosphate composite precursor is the one in air-flow crushing, mechanical crushing.Step 3) high speed batch mixing merge adopt be high speed mixer or fusion machine.
8. method according to claim 1, is characterized in that: described manganese source is the one of manganese monoxide, manganese dioxide, mangano-manganic oxide; Described source of iron is the one in di-iron trioxide, tri-iron tetroxide, or compound ferrimanganic source is oxalic acid ferromanganese, MnFe 2o 4; Described lithium source is at least one of lithium hydroxide, lithium carbonate; Described phosphorus source is at least one of ammonium phosphate, MAP, Diammonium phosphate (DAP), APP.
9. method according to claim 1, is characterized in that: step 3) in carbon source comprise organic carbon source, inorganic carbon source; Wherein step 1), 3) in organic carbon source be selected from one in starch, polyvinyl alcohol, polypropylene, phenolic resins, polystyrene, polyacrylonitrile, polyvinylpyrrolidone; Wherein, step 3) inorganic carbon source is one in superconduction carbon, conductive carbon fibre, carbon nano-tube; Described protective atmosphere is the one of argon gas, nitrogen.
10. the method according to any one of claim 1-9, is characterized in that: obtained lithium ion battery composite cathode material has the composite material of micro--Na dual structure, is the micron particles being obtained almost spherical by nano particle fusion growth.
CN201510847231.0A 2015-11-26 2015-11-26 Synthesis method of lithium ion battery composite cathode material LiMn1-xFexPO4/C Pending CN105355885A (en)

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CN107623107A (en) * 2017-10-16 2018-01-23 中南大学 A kind of method for preparing lithium manganese phosphate cell positive material
CN108172813A (en) * 2018-02-01 2018-06-15 广东工业大学 A kind of composite positive pole and preparation method thereof
CN109309228A (en) * 2017-07-28 2019-02-05 深圳市比亚迪锂电池有限公司 Positive electrode active materials, preparation method, anode and high-energy-density power battery
CN110828823A (en) * 2019-11-19 2020-02-21 湖北理工学院 Preparation method of lithium manganese borate/carbon composite material
CN110957490A (en) * 2019-07-30 2020-04-03 哈尔滨工业大学 Preparation method of carbon-coated sodium iron phosphate electrode material with hollow structure
CN111564622A (en) * 2020-07-14 2020-08-21 天能帅福得能源股份有限公司 Lithium manganese iron phosphate cathode material and preparation method thereof
CN112811406A (en) * 2021-01-11 2021-05-18 天津市捷威动力工业有限公司 Biosynthesis method of high-performance olivine type manganese-based phosphate positive electrode material
CN113942990A (en) * 2021-08-25 2022-01-18 北京当升材料科技股份有限公司 Lithium manganese iron phosphate precursor, lithium manganese iron phosphate positive electrode material, preparation method of lithium manganese iron phosphate positive electrode material, electrode and lithium ion battery
CN114249310A (en) * 2020-09-21 2022-03-29 中南大学 Lithium ion battery composite positive electrode material LiMn1-xFexPO4Method for synthesizing/C
CN115020664A (en) * 2022-06-17 2022-09-06 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
CN115196611A (en) * 2022-07-26 2022-10-18 江西赣锋锂电科技股份有限公司 Low-cost lithium iron phosphate and preparation method of lithium manganese iron phosphate
CN115432685A (en) * 2022-09-13 2022-12-06 广东邦普循环科技有限公司 Ferro-phosphorus lithium ion battery cathode material and preparation method and application thereof
WO2023184507A1 (en) * 2022-04-01 2023-10-05 宁德时代新能源科技股份有限公司 Positive electrode active material composition, positive electrode sheet, secondary battery, battery module, battery pack, and electric apparatus
WO2024087474A1 (en) * 2022-10-24 2024-05-02 广东邦普循环科技有限公司 Method for preparing lithium manganese iron phosphate positive electrode material by means of coprecipitation, and use thereof

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CN109309228A (en) * 2017-07-28 2019-02-05 深圳市比亚迪锂电池有限公司 Positive electrode active materials, preparation method, anode and high-energy-density power battery
CN109309228B (en) * 2017-07-28 2021-09-17 深圳市比亚迪锂电池有限公司 Positive electrode active material, preparation method, positive electrode and high-specific-energy power battery
CN107623107A (en) * 2017-10-16 2018-01-23 中南大学 A kind of method for preparing lithium manganese phosphate cell positive material
CN108172813B (en) * 2018-02-01 2020-12-08 广东工业大学 Composite cathode material and preparation method thereof
CN108172813A (en) * 2018-02-01 2018-06-15 广东工业大学 A kind of composite positive pole and preparation method thereof
CN110957490A (en) * 2019-07-30 2020-04-03 哈尔滨工业大学 Preparation method of carbon-coated sodium iron phosphate electrode material with hollow structure
CN110828823A (en) * 2019-11-19 2020-02-21 湖北理工学院 Preparation method of lithium manganese borate/carbon composite material
CN111564622A (en) * 2020-07-14 2020-08-21 天能帅福得能源股份有限公司 Lithium manganese iron phosphate cathode material and preparation method 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
CN112811406A (en) * 2021-01-11 2021-05-18 天津市捷威动力工业有限公司 Biosynthesis method of high-performance olivine type manganese-based phosphate positive electrode material
CN113942990A (en) * 2021-08-25 2022-01-18 北京当升材料科技股份有限公司 Lithium manganese iron phosphate precursor, lithium manganese iron phosphate positive electrode material, preparation method of lithium manganese iron phosphate positive electrode material, electrode and lithium ion battery
WO2023184507A1 (en) * 2022-04-01 2023-10-05 宁德时代新能源科技股份有限公司 Positive electrode active material composition, positive electrode sheet, secondary battery, battery module, battery pack, and electric apparatus
CN115020664A (en) * 2022-06-17 2022-09-06 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
CN115020664B (en) * 2022-06-17 2024-04-05 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
CN115196611A (en) * 2022-07-26 2022-10-18 江西赣锋锂电科技股份有限公司 Low-cost lithium iron phosphate and preparation method of lithium manganese iron phosphate
CN115432685A (en) * 2022-09-13 2022-12-06 广东邦普循环科技有限公司 Ferro-phosphorus lithium ion battery cathode material and preparation method and application thereof
CN115432685B (en) * 2022-09-13 2024-01-05 广东邦普循环科技有限公司 Ferrophosphorus lithium ion battery positive electrode material, and preparation method and application thereof
WO2024087474A1 (en) * 2022-10-24 2024-05-02 广东邦普循环科技有限公司 Method for preparing lithium manganese iron phosphate positive electrode material by means of coprecipitation, and use thereof

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