CN103247801A - Preparation method of high-conductivity lithium iron phosphate cathode material - Google Patents

Preparation method of high-conductivity lithium iron phosphate cathode material Download PDF

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CN103247801A
CN103247801A CN2013101529959A CN201310152995A CN103247801A CN 103247801 A CN103247801 A CN 103247801A CN 2013101529959 A CN2013101529959 A CN 2013101529959A CN 201310152995 A CN201310152995 A CN 201310152995A CN 103247801 A CN103247801 A CN 103247801A
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preparation
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范长岭
韩绍昌
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Hunan University
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention provides a preparation method of a high-conductivity lithium iron phosphate cathode material. The preparation method comprises the steps of: adding a doping compound into phosphoric acid and trivalent ferric salt solution, separately adding a pyrolytic carbon source and a carbonization accelerator in two manners, adding alkaline solution, controlling the pH of the system to be within 1-4, reacting for a period of time, washing and drying so as to obtain a ferric phosphate precursor; and mixing a lithium source, the precursor, the pyrolytic carbon source and the carbonization accelerator, stirring (or ball milling), drying in vacuum, thermally treating and grinding so as to prepare the doped carbon-wrapping lithium iron phosphate. The doping compound, the pyrolytic carbon source and the carbonization accelerator are added when the ferric phosphate precursor is prepared, the electric conductivity of lithium iron phosphate intracells and the electric conductivity among particles are improved, and the electrochemical performance of the lithium iron phosphate intracells is obviously improved at a high rate; and moreover, ferrous iron at high price is not used any more, so that the production cost is greatly lowered.

Description

A kind of preparation method of high conductivity lithium iron phosphate positive material
Technical field
The present invention relates to a kind of preparation method of anode material for lithium-ion batteries, particularly the preparation method of lithium iron phosphate positive material.
Background technology
The positive electrode active materials that lithium ion battery is commonly used has LiCoO 2, LiMn 2O 4And LiFePO 4, wherein, because plurality of advantages such as LiFePO 4 material has Stability Analysis of Structures, Heat stability is good, cost of material is low, toxicity is low, environmental friendliness, security performance is good and high-temperature behavior is good are a kind of very potential positive electrode active materials.Particularly its oxidation heat liberation temperature surpasses 400 ℃, has good thermal stability.
But LiFePO 4Electronic conductivity lower, only be 10 -9～10 -10S/cm, thereby high rate performance is poor, this has limited its application.Usually adopt bag carbon, coated with conductive material, ion and reduce method such as granular size and improve its conductance, improve chemical property mixes.At synthetic LiFePO 4Raw material in add materials such as phenolic resins, charcoal gel, glucose, citric acid, acetylene black, carbon black, graphite and Graphene, thereby they can form conduction when pyrolysis carbon improves LiFePO 4Conductance; Or adopt at LiFePO 4The surface coats Ag and the Fe of electrochemistry inertia 2Electric conducting materials such as P also can improve its conductance, improve chemical property.
To LiFePO 4Carry out carbon coated and can not only avoid Fe 3+Formation, can also obviously improve the conductance of its particle surface; But it can't improve LiFePO 4The conductance of intracell is therefore to LiFePO 4It is also very important to carry out ion doping.Many metal ions can be to LiFePO 4Mix, can stablize its crystal structure, improve electronics and Li +Migration, thereby improve its crystal the inner conductive rate, improve high rate performance.
Adopt the method for doped metal ion and carbon coated can improve its conductance, improve high rate performance.But at present general what adopt is+source of iron of divalent that its cost of material is higher, and follow-uply requires very high to heating furnace in the production process and protective gas.
Also there is research to report and adopts the carbon source reduction to hang down the presoma FePO of the trivalent of price 4Preparation LiFePO 4The method of/C can obviously reduce production costs.But most FePO that adopted pure phase 4, when mixing with the Li source, add doped chemical and carbon source, prepare the LiFePO that mixes and wrap carbon 4/ C; These doped chemicals and carbon source are enclosed in FePO 4The periphery, form LiFePO in follow-up heat treatment 4In the process of/C, it is to be difficult to a large amount of granule interior that enters that the inside of its core only depends on the diffusion of ion in the sintering process and carbon, only have the doped metallic elements of minute quantity and carbon source to enter the top layer, thereby conductance is not high; Although the chemical property when low range is also good, the performance than high magnification the time can not get basic improvement.
Summary of the invention
The present invention aims to provide and a kind ofly can effectively reduce production costs, prepare the method for the LiFePO4 with higher conductance and good high rate performance.Implementation of the present invention is as follows:
A kind of preparation method of lithium iron phosphate positive material, preparing two steps by presoma preparation and LiFePO4 forms, wherein the presoma preparation process is selected one of following dual mode, first kind of mode: phosphoric acid solution is mixed with ferric salt solution, in solution, add doping compound, RESEARCH OF PYROCARBON source compound and carbonization promoter compound afterwards; Afterwards with behind above-mentioned mixture system and the alkaline solution hybrid reaction certain hour, resulting powder obtains the ferric phosphate presoma through washing---drying, and the pH value of control reaction system is in 1～4 scope, and temperature is 50～80 ℃ scope; The second way: phosphoric acid solution is used compound with after ferric salt solution is mixed to wherein adding to mix; Afterwards above-mentioned mixture system is mixed with alkaline solution, again to wherein adding RESEARCH OF PYROCARBON source compound and carbonization promoter compound, behind the reaction certain hour, resulting powder is through washing---drying, obtain the ferric phosphate presoma, the pH value of control reaction system is in 1～4 scope, and temperature is 50～80 ℃ scope.Dual mode is adopted in the adding that is pyrolysis carbon-source cpd and carbonization promoter compound, and a kind of is to join in the mixed solution of phosphoric acid, trivalent iron salt and doped compound; Another kind is to join in the mixed system that contains alkaline solution.In the present invention, the carbonization promoter compound refers in the carbon-source cpd pyrolytic process, can accelerate the formation of carbon crystallite and regularly arranged material.Described alkaline solution generally adopts ammoniacal liquor or alkali hydroxide soln.
The LiFePO4 preparation process is: with lithium source and two kinds of materials of the resultant presoma of the first step by lithium atom: the mol ratio of iron atom (1～1.05): 1 prepares burden, and to wherein adding RESEARCH OF PYROCARBON source compound and carbonization promoter compound, gets mixed material again; Similar process in the preparation of existing LiFePO4 obtains lithium iron phosphate positive material, namely adopts one of following dual mode, and first kind (do and mix): ball milling---grind by vacuumize---heat treatment---; Second kind (wet mixing): add appropriate amount of organic in above-mentioned gained mixed material, behind stirring or the ball milling, vacuumize---heat treatment---is ground.
In mixed material, add appropriate amount of organic,---heat treatment---grinding through ball milling or stirring, vacuumize again.
Mixing with compound is one of following material or its mixture, the oxide of Mg, oxyhydroxide, chloride or organic compound; The oxide of Cr, oxyhydroxide, chloride or organic compound; The oxide of Ti, oxyhydroxide, chloride or organic compound; The oxide of Y, oxyhydroxide, chloride or organic compound; The oxide of Al, oxyhydroxide, chloride or organic compound; The oxide of La, oxyhydroxide, chloride or organic compound.Further, described doping is (0.005～0.05) with the ratio of the total mole number of foreign atom in the compound and Fe atomic molar number: 1.
The RESEARCH OF PYROCARBON source compound is selected one of following material or its mixture, polyvinyl alcohol, polyvinyl chloride, glucose, sucrose, phenolic resins, epoxy resin or ascorbic acid.The carbonization promoter compound is selected one of following material or its mixture, H 3BO 3, B 2O 3, B 4C, MnO 2, Al 2O 3, NiO, Si, SiC or SiO 2
The present invention compared with prior art, the advantage that has has:
1. the present invention just adds doped compound and pyrolysis carbon source in the process of preparation ferric phosphate presoma, thus guarantee its inside evenly mixed metal ion, disperseed pyrolytic carbon, greatly improved LiFePO 4The internal crystal framework conductance of/C has obviously improved its chemical property when high magnification.
2. add carbonization promoter and accelerated the pyrolysis of carbon source in the building-up process, prepared LiFePO 4Conductance reach higher 10 -1S/cm, its discharge capacity when 10C is 100mAh/g, has good high rate performance.
3. the present invention does not re-use the ferrous iron of high price, has greatly reduced the cost of raw material; Presoma with preparation prepares LiFePO in conjunction with the RESEARCH OF PYROCARBON reducing process 4/ C has reduced in the building-up process the requirement of firing equipment and protective atmosphere, has cut down production cost.
Embodiment
Embodiment 1
(1) configuration quality concentration is 75% H respectively 3PO 4Fe (the NO of solution, 1.5mol/L 3) 3The NaOH solution of solution, 6mol/L.
(2) with above-mentioned H 3PO 4Solution and Fe (NO 3) 3Solution 1:1 in molar ratio mixes, afterwards by the Mg:Fe atomic molar than being the ratio of 0.02:0.98, adding doped compound MgO presses and FePO 4Mass ratio be respectively 8% and 0.12% ratio, add pyrolysis carbon source polyvinyl alcohol and carbonization Urotropinum 3BO 3After stirring 30min, add in the reactor with NaOH solution, stir under the speed of 800r/min, control pH is 1.5, at 80 ℃ of reaction 5h.Afterwards sediment is filtered and with distilled water, ethanol clean to pH be 7, be drying to obtain presoma Fe 0.98Mg 0.02PO 4/ C(is the Fe that carbon coats 0.98Mg 0.02PO 4).
(3) Fe that lithium source material LiOH and last step are made 0.98Mg 0.02PO 4/ C presses the molar ratio ingredient of 1.03:1 in ball grinder, presses and LiFe again 0.98Mg 0.02PO 4The mass ratio of/C is respectively 2% and 0.04% ratio, adds polyvinyl alcohol and H 3BO 3, add an amount of absolute ethyl alcohol again, behind the ball milling 3h, in vacuum drying chamber in 80 ℃ of dry 12h.Then raw material is put into the tube type resistance furnace that is connected with Ar gas, be heated to 350 ℃ and be incubated 5h with the speed of 5 ℃/min; Be heated to 650 ℃ and be incubated 18h with the speed of 5 ℃/min again, cool to room temperature with the furnace.The sample of preparation is fully ground the back by 400 purpose standard screens with agate mortar in the glove box that is full of Ar gas, obtain Powdered positive electrode active materials LiFe 0.98Mg 0.02PO 4/ C.
Be solvent with N-methyl-pyrrolidones, active material, conductive agent acetylene black and binding agent polyvinylidene fluoride are carried out magnetic agitation by the mass ratio of 80:15:5, then slurry is coated on the aluminium foil, prepare the thick anode pole piece of 30 μ m, at 100 ℃ of inner drying 12h of vacuum drying chamber, in being full of the glove box of high-purity argon gas, carry out the assembling of 2016 batteries then.Electrolyte is 1mol/LLiPF 6/ EC+DMC+EMC(1:1:1, volume ratio), barrier film is Celgard2400.Battery is carried out the constant current charge-discharge test in the potential range of 2.5～4.1V.Investigate its discharge capacity when 0.1C and 10C, wherein 1C=170mA/g.Probe temperature is 25 ± 0.5 ℃.
Charge-discharge test is the result show, the conductance of above-mentioned active powder body material is 1.0 * 10 -1S/cm, the discharge capacity when 0.1C is 148mAh/g, the discharge capacity when 10C is 100mAh/g.
Comparative Examples 1
(1) configuration quality concentration is 75% H respectively 3PO 4Fe (the NO of solution, 1.5mol/L 3) 3The NaOH solution of solution, 6mol/L.
(2) with above-mentioned H 3PO 4Solution and Fe (NO 3) 3Solution 1:1 in molar ratio mixes, and behind the stirring 30min, adds in the reactor with NaOH solution, stirs under the speed of 800r/min, and control pH value is 1.5, at 80 ℃ of reaction 5h.Afterwards sediment is filtered and with distilled water, ethanol clean to pH be 7, be drying to obtain presoma FePO 4
(3) FePO that lithium source material LiOH and last step are made 4Press the molar ratio ingredient of 1.03:1 in ball grinder, than for the ratio of 0.02:0.98 adds doped compound MgO, add the polyvinyl alcohol with embodiment 1 same amount in the Mg:Fe atomic molar, prepare Powdered positive electrode active materials LiFe by the method for embodiment 1 0.98Mg 0.02PO 4/ C.
Charge-discharge test is the result show, the conductance of above-mentioned active powder body material is 1.1 * 10 -4S/cm, the discharge capacity when 0.1C is 145mAh/g, the discharge capacity when 10C is 52mAh/g.
Compare with the material of embodiment 1, both conductances have differed nearly 3 orders of magnitude, and the result shows in 10C multiplying power discharging capacity comparison, and Comparative Examples 1 material also only is half of embodiment 1.
Embodiment 2
(1) disposes 80% H respectively 3PO 4Fe (the NO of solution, 2.0mol/L 3) 3The NaOH solution of solution, 8mol/L;
(2) with above-mentioned H 3PO 4Solution and Fe (NO 3) 3Solution 1:1 in molar ratio mixes, in the Cr:Fe atomic molar than being the ratio of 0.02:0.97, with doped compound Cr 2O 3Join in the mixed solution, behind the stirring 30min, add in the reactor with NaOH solution, press and FePO 4Mass ratio be respectively 7% and 0.10% ratio, in mixed solution, add pyrolysis carbon source epoxy resin and carbonization accelerant B 2O 3Stir under the speed of 1000r/min, control pH value is 1.6, at 80 ℃ of reaction 5h; Afterwards sediment is filtered and with distilled water, ethanol clean to pH be 7, be drying to obtain presoma Fe 0.97Cr 0.02PO 4/ C.
(3) with lithium source material Li 2CO 3The presoma Fe that obtained with the last step 0.97Cr 0.02PO 4/ C presses the mixed in molar ratio of 0.52:1, presses and LiFe 0.97Cr 0.02PO 4The mass ratio of/C is respectively 3% and 0.06% ratio, adds epoxy resin and B 2O 3, obtain mixed material; To be added in the gained mixed material in the appropriate amount of organic acetone afterwards, stir 5h after, basic by the process conditions identical with embodiment 1, through vacuumize---heat treatment---grind and prepare powder body material LiFe 0.97Cr 0.02PO 4/ C.
Test result shows that the conductance of above-mentioned powder body material is 1.2 * 10 -1S/cm, the discharge capacity when 0.1C is 152mAh/g, the discharge capacity when 10C is 102mAh/g.
Embodiment 3
(1) disposes 70% H respectively 3PO 4The FeCl of solution, 1.8mol/L 3The NaOH solution of solution, 6mol/L;
(2) with above-mentioned H 3PO 4Solution and FeCl 3Solution 1:1 in molar ratio mixes, afterwards by the Ti:Fe atomic molar than being the ratio of 0.02:0.96, adding doped compound TiO in the mixed solution 2, join in the reactor with NaOH solution; Press again afterwards and FePO 4Mass ratio be respectively 6% and 0.08% ratio, add pyrolysis carbon source phenolic resins and carbonization accelerant B in the mixed system in the aforesaid reaction vessel 4C behind the stirring 30min, stirs under the speed of 1000r/min, and control pH value is 1.5, at 80 ℃ of reaction 5h.Sediment is filtered, with distilled water, ethanol clean to pH be 7, drying obtains presoma Fe 0.96Ti 0.02PO 4/ C.
(3) the presoma Fe that lithium source material LiF and last step are made 0.96Ti 0.02PO 4/ C prepares burden in ball grinder by the mixed in molar ratio of 1.05:1, presses and Fe 0.96Ti 0.02PO 4The mass ratio of/C is respectively 4% and 0.08% ratio, adds phenolic resins and B in ball grinder 4C adds an amount of absolute ethyl alcohol, the process conditions of pressing embodiment 1, and---vacuumize---heat treatment---is ground, and obtains LiFe through ball milling 0.96Ti 0.02PO 4/ C.
Test result shows that the conductance of above-mentioned powder body material is 1.8 * 10 -1S/cm, the discharge capacity when 0.1C is 150mAh/g, the discharge capacity when 10C is 105mAh/g.
Embodiment 4
(1) disposes 80% H respectively 3PO 4The FeCl of solution, 0.8mol/L 3The NaOH solution of solution, 8mol/L;
(2) with above-mentioned H 3PO 4Solution and FeCl 3Solution 1:1 in molar ratio mixes, afterwards by the Y:Fe atomic molar than being the ratio of 0.02:0.97, adding doped compound Y in the mixed solution 2O 3, behind the stirring 30min; Join in the reactor with NaOH solution again, press and FePO 4Mass ratio be respectively 8% and 0.12% ratio, add pyrolysis carbon source glucose and carbonization captax nO 2, under the speed of 800r/min, stirring, control pH value is 1.5, at 80 ℃ of reaction 8h.With sediment filter the back, with distilled water, ethanol clean to pH be 7, be drying to obtain presoma Fe 0.97Y 0.02PO 4/ C.
(3) the presoma Fe that lithium source material LiF and last step are made 0.97Y 0.02PO 4/ C prepares burden in ball grinder by the mixed in molar ratio of 1.04:1, presses and Fe 0.97Y 0.02PO 4The mass ratio of/C is respectively 2% and 0.04% ratio, adds glucose and MnO in ball grinder 2, add an amount of absolute ethyl alcohol, the process conditions of pressing embodiment 1,---vacuumize---heat treatment---is ground, and obtains LiFe through ball milling 0.97Y 0.02PO 4/ C.
Test result shows that the conductance of above-mentioned powder body material is 1.5 * 10 -1S/cm, the discharge capacity when 0.1C is 153mAh/g, the discharge capacity when 10C is 106mAh/g.
Embodiment 5
(1) disposes 70% H respectively 3PO 4The Fe of solution, 1.8mol/L 2(SO 4) 3The NaOH solution of solution, 6mol/L;
(2) with above-mentioned H 3PO 4Solution and Fe 2(SO 4) 3Solution 2:1 in molar ratio mixes, afterwards by the Al:Fe atomic molar than being the ratio of 0.02:0.97, adding doped compound Al in the mixed solution 2O 3, press again afterwards and FePO 4Mass ratio be respectively 7% and 0.10% ratio, in above-mentioned mixed solution, add pyrolysis carbon source ascorbic acid and carbonization accelerant A l 2O 3, behind the stirring 30min, join in the reactor with NaOH solution; Stir under the speed of 600r/min, control pH value is 1.5, at 80 ℃ of reaction 6h.With sediment filter the back, with distilled water, ethanol clean to pH be 7, be drying to obtain presoma Fe 0.97Al 0.02PO 4/ C.
(3) the presoma Fe that lithium source material LiOH and last step are made 0.97Al 0.02PO 4/ C prepares burden in ball grinder by the mixed in molar ratio of 1.05:1, presses and Fe 0.97Al 0.02PO 4The mass ratio of/C is respectively 3% and 0.06% ratio, adds ascorbic acid and Al in ball grinder 2O 3, add an amount of absolute ethyl alcohol, the process conditions of pressing embodiment 1,---vacuumize---heat treatment---is ground, and obtains LiFe through ball milling 0.97Al 0.02PO 4/ C.
Test result shows that the conductance of above-mentioned powder body material is 1.6 * 10 -1S/cm, the discharge capacity when 0.1C is 151mAh/g, the discharge capacity when 10C is 105mAh/g.
Embodiment 6
(1) disposes 75% H respectively 3PO 4The Fe of solution, 1.5mol/L 2(SO 4) 3The NaOH solution of solution, 8mol/L;
(2) with above-mentioned H 3PO 4Solution and Fe 2(SO 4) 3Solution 2:1 in molar ratio mixes, afterwards in the ratio of La:Fe atomic molar than 0.02:0.97, with doped compound La 2O 3Join in the mixed solution, press and FePO 4Mass ratio be respectively 6% and 0.09% ratio, add pyrolysis carbon source sucrose and carbonization promoter SiO in the mixed solution 2After stirring 30min, add in the reactor with NaOH solution, stir under the speed of 600r/min, control pH value is 1.6, at 80 ℃ of reaction 6h; Afterwards sediment is filtered and with distilled water, ethanol clean to pH be 7, be drying to obtain presoma Fe again 0.97La 0.02PO 4/ C.
(3) with lithium source material Li 2CO 3The presoma Fe that obtained with the last step 0.97La 0.02PO 4/ C presses the mixed in molar ratio of 0.52:1, presses and Fe 0.97La 0.02PO 4The mass ratio of/C is respectively 4% and 0.08% ratio, adds pyrolysis carbon source sucrose and carbonization promoter SiO 2, obtain mixed material; To be added in the gained mixed material in the appropriate amount of organic acetone afterwards, stir 8h after, basic by the process conditions identical with embodiment 1, through vacuumize---heat treatment---grind and prepare powder body material LiFe 0.97Cr 0.02PO 4/ C.
Test result shows that the conductance of above-mentioned powder body material is 1.4 * 10 -1S/cm, the discharge capacity when 0.1C is 153mAh/g, the discharge capacity when 10C is 102mAh/g.

Claims (6)

1. the preparation method of a LiFePO 4 material prepares two steps by presoma preparation and LiFePO4 and forms, and it is characterized in that: the presoma preparation process is selected one of following dual mode,
First kind of mode: phosphoric acid solution is mixed with ferric salt solution, in mixed solution, add doping compound, RESEARCH OF PYROCARBON source compound and carbonization promoter compound again; Afterwards with behind above-mentioned mixture system and the alkaline solution hybrid reaction certain hour, resulting powder obtains the ferric phosphate presoma through washing---drying, and the pH value of control reaction system is in 1～4 scope, and temperature is 50～80 ℃ scope;
The second way: phosphoric acid solution is mixed with ferric salt solution, use compound to wherein adding to mix again; Afterwards above-mentioned mixture system is mixed with alkaline solution, again to wherein adding RESEARCH OF PYROCARBON source compound and carbonization promoter compound, behind the reaction certain hour, resulting powder is through washing---drying, obtain the ferric phosphate presoma, the pH value of control reaction system is in 1～4 scope, and temperature is 50～80 ℃ scope;
The LiFePO4 preparation process is: with lithium source and two kinds of materials of the resultant presoma of the first step by lithium atom: the mol ratio of iron atom (1～1.05): 1 prepares burden, and to wherein adding RESEARCH OF PYROCARBON source compound and carbonization promoter compound, gets mixed material again;---vacuumize---heat treatment---is ground can to adopt one of following dual mode to obtain the iron phosphate powder material that nano-sized carbon coats, first kind: ball milling afterwards; Second kind: add appropriate amount of organic in above-mentioned gained mixed material, behind stirring or the ball milling, vacuumize---heat treatment---is ground.
2. the preparation method of LiFePO 4 material as claimed in claim 1, it is characterized in that: described doping compound is one of following material or its mixture, the oxide of Mg, oxyhydroxide, chloride or organic compound; The oxide of Cr, oxyhydroxide, chloride or organic compound; The oxide of Ti, oxyhydroxide, chloride or organic compound; The oxide of Y, oxyhydroxide, chloride or organic compound; The oxide of Al, oxyhydroxide, chloride or organic compound; The oxide of La, oxyhydroxide, chloride or organic compound.
3. the preparation method of LiFePO 4 material as claimed in claim 2 is characterized in that: described doping is (0.005～0.05) with the ratio of the total mole number of foreign atom in the compound and Fe atomic molar number: 1.
4. as the preparation method of the described LiFePO 4 material of one of claim 1～3, it is characterized in that: described RESEARCH OF PYROCARBON source compound is selected one of following material or its mixture, polyvinyl alcohol, polyvinyl chloride, glucose, sucrose, phenolic resins, epoxy resin or ascorbic acid.
5. as the preparation method of the described LiFePO 4 material of one of claim 1～3, it is characterized in that: described carbonization promoter compound is selected one of following material or its mixture, H 3BO 3, B 2O 3, B 4C, MnO 2, Al 2O 3, NiO, Si, SiC or SiO 2
6. the preparation method of LiFePO 4 material as claimed in claim 4 is characterized in that: one of following material of described carbonization promoter compound selection or its mixture, H 3BO 3, B 2O 3, B 4C, MnO 2, Al 2O 3, NiO, Si, SiC or SiO 2
CN2013101529959A 2013-04-27 2013-04-27 Preparation method of high-conductivity lithium iron phosphate cathode material Pending CN103247801A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105129761A (en) * 2015-08-31 2015-12-09 无锡市嘉邦电力管道厂 Method for preparing ferrous phosphate positive pole material
CN110600705A (en) * 2019-09-20 2019-12-20 程立勋 Preparation method of battery positive electrode material
CN111029571A (en) * 2019-11-22 2020-04-17 贵州唯特高新能源科技有限公司 Preparation method of silicon dioxide uniformly doped iron phosphate
CN111224084A (en) * 2020-01-13 2020-06-02 合肥国轩高科动力能源有限公司 Lithium iron phosphate/lithium silicate composite material and preparation method and application thereof

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US20090183650A1 (en) * 2006-06-12 2009-07-23 The Regents Of The University Of California Optimization of carbon coatings
CN102275893A (en) * 2011-07-20 2011-12-14 湖南维邦新能源有限公司 Method for preparing lithium iron phosphate and lithium iron phosphate resulting thereby
CN102468480A (en) * 2010-11-19 2012-05-23 北京有色金属研究总院 Preparation method of high-rate capacity lithium iron phosphate material
CN102856545A (en) * 2012-09-11 2013-01-02 清华大学 Preparation method of micro-nano-grade metal-ion-doped lithium iron phosphate anode material

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20090183650A1 (en) * 2006-06-12 2009-07-23 The Regents Of The University Of California Optimization of carbon coatings
CN102468480A (en) * 2010-11-19 2012-05-23 北京有色金属研究总院 Preparation method of high-rate capacity lithium iron phosphate material
CN102275893A (en) * 2011-07-20 2011-12-14 湖南维邦新能源有限公司 Method for preparing lithium iron phosphate and lithium iron phosphate resulting thereby
CN102856545A (en) * 2012-09-11 2013-01-02 清华大学 Preparation method of micro-nano-grade metal-ion-doped lithium iron phosphate anode material

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105129761A (en) * 2015-08-31 2015-12-09 无锡市嘉邦电力管道厂 Method for preparing ferrous phosphate positive pole material
CN110600705A (en) * 2019-09-20 2019-12-20 程立勋 Preparation method of battery positive electrode material
CN111029571A (en) * 2019-11-22 2020-04-17 贵州唯特高新能源科技有限公司 Preparation method of silicon dioxide uniformly doped iron phosphate
CN111029571B (en) * 2019-11-22 2021-06-11 贵州唯特高新能源科技有限公司 Preparation method of silicon dioxide uniformly doped iron phosphate
CN111224084A (en) * 2020-01-13 2020-06-02 合肥国轩高科动力能源有限公司 Lithium iron phosphate/lithium silicate composite material and preparation method and application thereof
CN111224084B (en) * 2020-01-13 2022-04-12 合肥国轩高科动力能源有限公司 Lithium iron phosphate/lithium silicate composite material and preparation method and application thereof

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Application publication date: 20130814