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CN106602060A - Low-cost lithium iron phosphate material, and preparation method and application thereof - Google Patents

Low-cost lithium iron phosphate material, and preparation method and application thereof Download PDF

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Publication number
CN106602060A
CN106602060A CN201611219247.8A CN201611219247A CN106602060A CN 106602060 A CN106602060 A CN 106602060A CN 201611219247 A CN201611219247 A CN 201611219247A CN 106602060 A CN106602060 A CN 106602060A
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Prior art keywords
source
lithium
atmosphere
iron
mixture
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CN201611219247.8A
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Inventor
席小兵
张怀文
赵玉萌
庞钧友
黄友元
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Bate Rui (tianjin) Nano Material Manufacturing Co Ltd
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Bate Rui (tianjin) Nano Material Manufacturing Co Ltd
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Priority to CN201611219247.8A priority Critical patent/CN106602060A/en
Publication of CN106602060A publication Critical patent/CN106602060A/en
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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
    • H01M4/58—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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B25/00—Phosphorus; Compounds thereof
    • C01B25/16—Oxyacids of phosphorus; Salts thereof
    • C01B25/26—Phosphates
    • C01B25/45—Phosphates containing plural metal, or metal and ammonium
    • 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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • H01M10/0587—Construction or manufacture of accumulators having only wound construction elements, i.e. wound positive electrodes, wound negative electrodes and wound separators
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2220/00—Batteries for particular applications
    • H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention discloses a low-cost lithium iron phosphate material, and a preparation method and an application thereof. The preparation method comprises the steps of 1) mixing a lithium source, an iron source, a phosphorus source and optional doped elements to obtain a material, adding a carbon source and a solvent for grinding and drying to obtain a precursor; 2) smashing the precursor in a condition of adding auxiliaries; 3) performing briquetting on the material obtained by smashing; and 4) putting the briqueted material into a reaction furnace, heating in an inert atmosphere and performing constant-temperature roasting, and smashing to obtain the lithium iron phosphate material. By adoption of the method for preparing the lithium iron phosphate material, the manufacturing cost is remarkably lowered, and the equipment yield is obviously increased; in addition, a battery, which is prepared by taking the lithium iron phosphate material as a positive electrode active material, has excellent electrochemical property; the discharge capacity at 1C is greater than 140.2mAh/g; and the number of cycles is greater than 3,640 when the cycling capacity is less than or equal to 80% of the capacity average value in the last three weeks.

Description

A kind of inexpensive LiFePO 4 material, Preparation Method And The Use
Technical field
The invention belongs to electrode material synthesis field, is related to a kind of LiFePO 4 material, Preparation Method And The Use, especially It is related to a kind of LiFePO 4 material, its preparation method and the purposes for lithium ion battery.
Background technology
As the lithium iron phosphate positive material for possessing olivine structural and other traditional lithium ion secondary battery positive electrode materials The LiMn of material such as spinel structure2O4With the LiCoO of layer structure2Compare, the raw material sources of LiFePO4 extensively, price more Cheap and environmentally safe, and the material possesses good security performance and longer cycle life.
LiFePO4 industry was increasingly becoming the head of main flow electric automobile, energy-accumulating power station through development for many years in nearly 20 years Material selection, is especially increasingly subject to social concerns instantly in current environment, makes and develop one health, environmentally friendly livable Environment becomes everybody common recognition, since 2013, National Development and Reform Committee, the Ministry of Finance, Ministry of Industry and Information and Deng Ge great ministries and commissions of the Department of Science and Technology A series of encouragement have been put into effect successively and have promoted the policy of new-energy automobile development, including the great number in new-energy automobile acquisition price Subsidy, and the not policy favour such as restricting the number of not restricting driving, new forms of energy industry welcome explosive growth in 2015.
At present the cost of electronic battery is overall higher, and this will certainly affect electronic battery in the extensive general of civil area And, thus reduce electrokinetic cell cost it is imperative, wherein as positive electrode LiFePO4 occupy electrokinetic cell into This 35%～45%, thus the cost for how effectively reducing LiFePO4 becomes future influence electrokinetic cell pass fully under way Key, Low-cost lithium iron phosphate positive material and preparation method thereof possess profound significance.
The A of CN 105253870 disclose a kind of LiFePO4 production technology, including step：1) raw material detection is carried out；2) Iron phosphate is carried out into drying eliminating water；3) mixing treatment is carried out using grinder；4) material dispersion process is carried out using dispersion machine；5) Carry out spray drying treatment；6) hydraulic press material briquetting charging process is carried out；7) pusher furnace sintering processes are carried out；8) roll-in is carried out Fine grinding is processed；9) sieved, packed, being checked, warehouse-in is processed.The method has technological design rationally, production efficiency and quality Higher advantage, but, adopt the LiFePO4 that the method prepares performance need to be further improved with meet it is actual should Demand.
The content of the invention
For the above-mentioned problems in the prior art, it is an object of the invention to provide a kind of low cost and excellent performance LiFePO 4 material, Preparation Method And The Use.Not only preparation cost is cheap for the LiFePO 4 material of the present invention, and, adopt The electrochemistry of positive pole and the battery being further assembled into is made as positive electrode active materials with the LiFePO 4 material of the present invention Can be excellent, the discharge capacity of 1C is recycled to meansigma methodss≤80% of the circulation volume than first three weeks capacity in more than 140.2mAh/g When cycle more than 3640 times.
" inexpensive LiFePO4 " of the present invention refers to：Sintering is lifted by way of briquetting and addition auxiliary agent combine The loadings of kiln and shorten the sintering time of kiln so that the preparation cost of LiFePO4 is lower, loaded by the manner crucible Amount lifts more than 75%, and sintering time shortens more than 4 hours, reduces energy consumption and cost.
It is that, up to above-mentioned purpose, the present invention is adopted the following technical scheme that：
In a first aspect, the present invention provides a kind of preparation method of LiFePO 4 material, the method comprising the steps of：
(1) lithium source, source of iron, phosphorus source and optional doped chemical source are mixed to get into material, add carbon source and solvent to carry out Grinding, is then dried, and obtains presoma；
(2) presoma that step (1) is obtained is crushed under conditions of auxiliary agent is added；
(3) crushing the material for obtaining to step (2) carries out briquetting, obtains the material after briquetting；
(4) material after the briquetting for obtaining step (3) is placed in reacting furnace, is heated up under inert atmosphere and constant temperature roasting Burn, crush, obtain LiFePO 4 material；
Wherein, the auxiliary agent is oxalic acid and/or ammonium oxalate.
Preferably, step (1) lithium source, source of iron, phosphorus source and optional doped chemical source are according to elemental lithium:Ferrum element: P elements:The mol ratio (0.95～1.05) of doped chemical:(0.95～1.05):(0.95～1.05):(0～0.05) is mixed Close, molar ratio such as can be 0.95:1:0.95:0、0.95:1:0.96:0、0.98:1:1:0.03、0.95:0.97:1:0.02、 1:0.98:1:0、0.97:0.96:1:0.04、1:1:0.95:0、1:1:1:0、1:1:1:0.01、1:1:1:0.03、1:1:1: 0.05、0.95:1:1:0.025 or 1:1:0.96:0.01 etc..
Heretofore described " optional doped chemical source " refers to：Doped chemical source can be added, it is also possible to without doping Element source.
Preferably, step (1) lithium source includes lithium carbonate, Lithium hydrate, lithium dihydrogen phosphate, lithium nitrate, lithium oxalate, vinegar In sour lithium or Lithium Citrate de any one or at least two mixture, mixture typical case but non-limiting examples have： The mixture of the mixture of Lithium hydrate and lithium dihydrogen phosphate, lithium dihydrogen phosphate and Lithium Citrate de, Lithium hydrate and lithium nitrate The mixture of mixture, lithium dihydrogen phosphate and lithium oxalate, the mixture of Lithium hydrate, lithium dihydrogen phosphate and lithium nitrate, lithium nitrate, Mixture of lithium oxalate and lithium acetate etc..But be not limited to the above-mentioned lithium source enumerated, other are commonly used in the art can reach it is identical The lithium source of effect can also be used for the present invention.
Preferably, step (1) source of iron is included in iron phosphate, Ferrox., iron acetate, iron sesquioxide or ferric nitrate Any one or at least two mixture, mixture typical case but non-limiting examples have：Iron phosphate and Ferrox. Mixture, the mixture of iron phosphate and iron acetate, the mixture of iron acetate and iron sesquioxide, iron phosphate, Ferrox. and The mixture of iron acetate, mixture of iron phosphate, iron acetate and ferric nitrate etc..But the above-mentioned source of iron enumerated is not limited to, other The source of iron that can reach same effect commonly used in the art can also be used for the present invention.
Preferably, step (1) phosphorus source include phosphoric acid, ammonium dihydrogen phosphate, diammonium phosphate, ammonium phosphate, iron phosphate or In lithium dihydrogen phosphate any one or at least two mixture, mixture typical case but non-limiting examples have：Phosphoric acid With the mixture of the mixture of the mixture of ammonium dihydrogen phosphate, phosphoric acid and diammonium phosphate, ammonium dihydrogen phosphate and diammonium phosphate, The mixture of the mixture of ammonium phosphate and iron phosphate, ammonium dihydrogen phosphate and iron phosphate, diammonium phosphate and lithium dihydrogen phosphate it is mixed Compound, but the above-mentioned phosphorus source enumerated is not limited to, other phosphorus sources that can reach same effect commonly used in the art can also be used for this Invention.
Preferably, step (1) the doped chemical source includes zinc source, manganese source, Tong Yuan, magnesium source, titanium source, zirconium source, silicon source, vanadium In source, chromium source, niobium source any one or at least two combination.
Preferably, step (1) carbon source include glucose, sucrose, citric acid, Polyethylene Glycol, polyvinyl alcohol, starch or In cyclodextrin any one or at least two mixture, mixture typical case but non-limiting examples have：Glucose and The mixture of the mixture of sucrose, the mixture of Fructus Vitis viniferae sugar and starch, glucose and citric acid, glucose and Polyethylene Glycol it is mixed The mixture of the mixture of compound, sucrose and citric acid, Polyethylene Glycol and polyvinyl alcohol, glucose, sucrose and citric acid it is mixed Compound, the mixture of glucose, citric acid and Polyethylene Glycol, glucose, sucrose, citric acid, Polyethylene Glycol and polyvinyl alcohol Mixture etc..
Preferably, with the gross mass of step (1) material as 100% meter, the mass percent of step (1) carbon source For 1%～20%, for example, 1%, 2%, 4%, 5%, 7%, 9%, 10%, 12%, 14%, 15%, 16%, 18%, 18.5% or 20% etc..
Preferably, step (1) solvent in water, methanol, ethanol, acetone or the isopropanol any one or at least Two kinds of mixture.
Preferably, with the gross mass of step (1) material as 100% meter, the mass percent of step (1) solvent For 40%～50%, for example, 40%, 41.5%, 42%, 43%, 44%, 45%, 46%, 47%, 48%, 49% or 50% Deng.
Preferably, the mode of step (1) the addition carbon source and solvent is：It is initially charged after carbon source and adds solvent.
Preferably, for ball milling, the time of the ball milling is 3h～5h to step (1) mode for adopting of grinding, for example, 3h, 3.3h, 3.4h, 3.5h, 3.6h, 3.7h, 3.85h, 4h, 4.1h, 4.2h, 4.3h, 4.5h, 4.8h, 4.9h or 5h etc..
Preferably, the mode that step (1) drying is adopted is spray drying.
Preferably, the device for adopting that is spray-dried is for enclosed spray dryer.
Preferably, when being spray-dried, the temperature of air inlet is 220 DEG C～280 DEG C, for example, 220 DEG C, 225 DEG C, 228 DEG C, 230 DEG C, 235 DEG C, 240 DEG C, 245 DEG C, 250 DEG C, 255 DEG C, 260 DEG C, 265 DEG C, 270 DEG C, 275 DEG C or 280 DEG C etc..
Preferably, when being spray-dried, the temperature of air outlet is 70 DEG C～90 DEG C, for example, 70 DEG C, 73 DEG C, 75 DEG C, 78 DEG C, 80 DEG C, 82 DEG C, 84 DEG C, 86 DEG C, 88 DEG C or 90 DEG C etc..
In the present invention, the auxiliary agent that step (2) is added is oxalic acid and/or ammonium oxalate.
" oxalic acid and/or ammonium oxalate " of the present invention refers to：Can be oxalic acid, or ammonium oxalate, can also be oxalic acid With the mixture of ammonium oxalate.
Preferably, the addition of step (2) auxiliary agent is the 1%～10% of forerunner's weight, for example, 1%, 2%th, 3%, 3.5%, 4%, 5%, 6%, 7%, 8%, 8.5%, 9% or 10% etc..
Preferably, the described crushing of step (2) is comminution by gas stream.
Preferably, step (2) device for adopting of crushing is for jet mill.
Preferably, step (2) D50 for being crushed to the material for obtaining is 1 μm～6 μm.
Preferably, the device that step (3) briquetting is adopted is for isostatic pressing machine.
Preferably, pressure during step (3) briquetting be 200MPa～300MPa, for example, 200MPa, 210MPa, 220MPa, 225MPa, 235MPa, 245MPa, 255MPa, 260MPa, 270MPa, 280MPa, 290MPa or 300MPa etc..
Step (4) inert atmosphere is nitrogen atmosphere, helium atmosphere, neon atmosphere, argon gas atmosphere, Krypton atmosphere, xenon The combination of any one or at least two atmosphere in gas atmosphere or carbon dioxide atmosphere.
Preferably, the speed of step (4) intensification is 2 DEG C/min～20 DEG C/min, for example, 2 DEG C/min, 4 DEG C/ min、5℃/min、6℃/min、8℃/min、10℃/min、11℃/min、12℃/min、13℃/min、15℃/min、16 DEG C/min, 17 DEG C/min, 18 DEG C/min, 19 DEG C/min or 20 DEG C/min etc..
Preferably, the temperature of step (4) constant temperature calcining be 600 DEG C～750 DEG C, such as 600 DEG C, 620 DEG C, 630 DEG C, 640 DEG C, 650 DEG C, 660 DEG C, 670 DEG C, 680 DEG C, 700 DEG C, 715 DEG C, 730 DEG C, 740 DEG C or 750 DEG C etc..
Preferably, the time of step (4) constant temperature calcining be 2h～6h, such as 2h, 2.5h, 3h, 3.2h, 3.4h, 3.6h, 4h, 4.3h, 4.5h, 4.7h, 5h, 5.25h, 5.5h, 5.8h or 6h etc..
Atmosphere during step (4) constant temperature calcining of the present invention is still inert atmosphere.
Preferably, step (4) the broken device for adopting is for jaw crusher.
Second aspect, the LiFePO 4 material that a kind of employing first aspect methods described of the invention is prepared.
The third aspect, the present invention provides a kind of positive pole, comprising the phosphorus described in second aspect in the raw material components of the positive pole Sour ferrum lithium is used as positive electrode active materials.
Fourth aspect, the present invention provides a kind of lithium ion battery, and the lithium ion battery includes the phosphorus described in second aspect Sour ferrum lithium material.
Compared with the prior art, the present invention has the advantages that：
(1) present invention is to presoma under conditions of auxiliary agent is added by crushing, then using isostatic pressing machine by thing Material briquetting in bulk, the roasting under inert atmosphere, then crush, prepare LiFePO 4 material.The present invention is in comminution by gas stream forerunner Auxiliary agent is added during body, while crushing ferric lithium phosphate precursor, the micro- of ferric lithium phosphate precursor and auxiliary agent is realized Meter level mixes, and auxiliary agent is filled between particles, and, the micron of auxiliary agent different in the structure of particle surface from traditional liquid phase coating Level filled type mixing can play extraordinary pore-creating and iris action in roasting process, while conduction of heat is substantially improved Growing up, alleviating hardened phenomenon of the lump material in roasting process for granule is significantly intercepted, contributes to the lifting of chemical property.
The present invention after lithium iron phosphate particles and the mixing of auxiliary agent micron order, using isostatic pressing machine briquetting into block, Neng Gouyou Effect reduces the contact gap of presoma material, heat conduction efficiency, shortening roasting time of the significant increase material in roasting process And the loadings of the single crucible of lifting, the production efficiency of kiln is greatly promoted, significantly reduce manufacturing cost.
(2) the LiFePO 4 material excellent performance that the present invention is prepared, prepares positive pole and goes forward side by side as positive electrode active materials The battery that one step is assembled into has excellent chemical property, and the discharge capacity of 1C is recycled to circulation in more than 140.2mAh/g Cycle during meansigma methodss≤80% of Capacity Ratio first three weeks capacity is more than 3640 times.
Description of the drawings
Fig. 1 is the SEM figures of LiFePO 4 material prepared by the embodiment of the present invention 1；
Fig. 2 is the SEM figures of LiFePO 4 material prepared by comparative example of the present invention 1.
Specific embodiment
Further illustrate technical scheme below in conjunction with the accompanying drawings and by specific embodiment.
Embodiment 1
By lithium carbonate, iron phosphate according to mol ratio 1.05:1 is mixed, then Li:Fe:P=1.05:1:1, first according to thing 10% addition glucose of material gross mass, then according to 50% addition deionized water of the material gross mass being mixed to get carries out ball Mill, takes out slurry after 5h, be dried with enclosed spray dryer, and intake air temperature arranges 280 DEG C, and air outlet temperature arranges 80 DEG C, material A is obtained, material A is crushed, oxalic acid is added according to the 1% of material A gross mass while crushing, crush Into material B is obtained, material B is carried out into briquetting with isostatic pressing machine, pressure is 200MPa, obtains lump material C, by lump material C Heated up with the rate of heat addition of 2 DEG C/min in a nitrogen atmosphere, continued in a nitrogen atmosphere in 750 DEG C of constant temperature calcining 2h, obtained To block lithium iron phosphate positive material, by block LiFePO4 with being crushed after jaw crushing crusher machine, powder phosphorus is obtained Sour ferrum lithium material.
Fig. 1 is the SEM figures of LiFePO 4 material manufactured in the present embodiment, as seen from the figure, manufactured in the present embodiment Grain is uniform in size, and concordance is preferable.
Embodiment 2
By lithium carbonate, iron sesquioxide, ammonium dihydrogen phosphate according to mol ratio 1.05:1:1.05 are mixed, then Li:Fe:P =1.05:1:1.05, first polyvinyl alcohol is added according to the 1% of the material gross mass being mixed to get, then according to material gross mass 50% addition ethanol carry out ball milling, slurry is taken out after 5h, be dried with enclosed spray dryer, intake air temperature arrange 220 DEG C, air outlet temperature arranges 75 DEG C, obtains material A, and material A is crushed, according to the total matter of material A while crushing 6.5% addition ammonium oxalate of amount, crushing completes to obtain material B, and material B is carried out into briquetting with isostatic pressing machine, and pressure is 300MPa, Lump material C is obtained, lump material C is heated up under an argon atmosphere with the rate of heat addition of 10 DEG C/min, continued in nitrogen In 720 DEG C of constant temperature calcining 4h under atmosphere, block lithium iron phosphate positive material is obtained, block LiFePO4 is broken with jaw crusher Crushed after broken, obtained powder LiFePO 4 material.
Embodiment 3
Lithium dihydrogen phosphate, Ferrox., titanium dioxide are compared into 0.95 according to you:1:0.02 is mixed, then Li:Fe:P: Ti=0.95:1:0.95:0.02, Polyethylene Glycol is added according to the 20% of the material gross mass being mixed to get, according to the total matter of material 50% addition acetone of amount carries out ball milling, and slurry is taken out after 5h, is dried with enclosed spray dryer, and intake air temperature is arranged 220 DEG C, air outlet temperature arranges 75 DEG C, obtains material A, and material A is crushed, according to the total matter of material A while crushing 10% addition ammonium oxalate of amount, crushing completes to obtain material B, and material B is carried out into briquetting with isostatic pressing machine, and pressure is 250MPa, Lump material C is obtained, lump material C is heated up in a nitrogen atmosphere with the rate of heat addition of 5 DEG C/min, continued in nitrogen gas In 600 DEG C of constant temperature calcining 6h under atmosphere, block lithium iron phosphate positive material is obtained, by block LiFePO4 jaw crushing crusher machine After crushed, obtain powder LiFePO 4 material.
Embodiment 4
By Lithium hydrate, Ferrox., phosphoric acid and magnesium oxide according to mol ratio 1.05:1:1:0.01 is mixed, then Li: Fe:P:Mg=1.05:1:1:0.01, first sucrose is added according to the 5% of the material gross mass being mixed to get, then according to material is total 45% addition methanol of quality carries out ball milling, and slurry is taken out after 4.5h, is dried with enclosed spray dryer, intake air temperature 260 DEG C are arranged, air outlet temperature arranges 75 DEG C, obtains material A, and material A is crushed, according to material A while crushing 3% addition oxalic acid of gross mass, crushing completes to obtain material B, and material B is carried out into briquetting with isostatic pressing machine, and pressure is 220MPa, Lump material C is obtained, lump material C is heated up under an argon atmosphere with the rate of heat addition of 15 DEG C/min, continued in argon In 750 DEG C of constant temperature calcining 6h under atmosphere, block lithium iron phosphate positive material is obtained, block LiFePO4 is broken with jaw crusher Crushed after broken, obtained powder LiFePO 4 material.
Embodiment 5
By carbonic acid dihydro lithium, iron acetate, ammonium phosphate and manganese acetate according to mol ratio 1:1:0.98:0.03 is mixed, then Li:Fe:P:Mn=1:1:0.98:0.03, first citric acid is added according to the 15% of the material gross mass being mixed to get, then according to 43% addition isopropanol of material gross mass carries out ball milling, and slurry is taken out after 4h, is dried with enclosed spray dryer, air intake Mouthful 250 DEG C of temperature setting, air outlet temperature arranges 70 DEG C, obtains material A, and material A is crushed, while crushing according to 5% addition ammonium oxalate of material A gross mass, crushing completes to obtain material B, and material B is carried out into briquetting with isostatic pressing machine, and pressure is 245MPa, obtains lump material C, and lump material C is heated up under an argon atmosphere with the rate of heat addition of 20 DEG C/min, continues Under an argon atmosphere in 730 DEG C of constant temperature calcining 5h, block lithium iron phosphate positive material is obtained, block LiFePO4 is broken with jaw Crushed after broken crusher machine, obtained powder LiFePO 4 material.
Embodiment 6
By lithium nitrate, iron phosphate and manganese oxalate according to mol ratio 0.96:1:0.04 is mixed, then Li:Fe:P:Mn= 0.96:1:1:0.04, first polyvinyl alcohol is added according to the 8.5% of the material gross mass being mixed to get, then according to the total matter of material 48% addition ethanol of amount carries out ball milling, and slurry is taken out after 3.5h, is dried with enclosed spray dryer, and intake air temperature sets 235 DEG C are put, air outlet temperature arranges 70 DEG C, obtains material A, and material A is crushed, it is total according to material A while crushing 7.5% addition oxalic acid of quality, crushing completes to obtain material B, and material B is carried out into briquetting with isostatic pressing machine, and pressure is 280MPa, Lump material C is obtained, lump material C is heated up under an argon atmosphere with the rate of heat addition of 5 DEG C/min, continued in argon gas In 650 DEG C of constant temperature calcining 3h under atmosphere, block lithium iron phosphate positive material is obtained, by block LiFePO4 jaw crushing crusher machine After crushed, obtain powder LiFePO 4 material.
Comparative example 1
By lithium dihydrogen phosphate, iron sesquioxide, niobium pentaoxide in molar ratio 1.05:1:0.01 mixes, then Li:Fe:P: Nb=1.05:1:1.05:0.01, mixed according to 15% addition sucrose of the material gross mass being mixed to get, and by material 50% addition ethanol of gross mass carries out ball milling, and slurry is taken out after 5h, is dried with enclosed spray drying agent, intake air temperature 220 DEG C are arranged, air outlet temperature arranges 75 DEG C, by the powder body after spray drying in N2The lower 700 DEG C of constant temperature 10h of atmosphere obtain phosphoric acid Ferrum lithium material, the material pulverizer after burning till obtains powder LiFePO 4 material after crushing.
Fig. 2 is the SEM figures of LiFePO 4 material prepared by this comparative example, as seen from the figure, material prepared by comparative example Even particle size degree is poor, and bulky grain is more, can reduce the chemical property of material.
The loadings and firing time contrast of the embodiment of table 1 and comparative example
The crucible loadings by the way of the manner is more traditional are can be seen that from data in table 1 lift more than 75%, sintering Time shortens more than 4 hours, so as to reduce energy consumption and cost.
Electrochemical property test
(1) preparation of battery
The preparation of positive pole：
Using the LiFePO 4 material of embodiment 1-6 and comparative example 1 as positive electrode active materials, respectively by 93g positive-actives Material LiFePO4, 3g binding agent Kynoar (PVDF) and 4g conductive agent acetylene blacks be added to 100gN- methyl pyrrolidones In, then stirring forms uniform anode sizing agent in de-airing mixer.The anode sizing agent is uniformly coated to into thickness for 16 μ The both sides of the aluminium foil of m, then drying, roll-in at 120 DEG C, the positive pole that prepared size is 540 × 43.5mm is cut, wherein containing about 6g positive electrode active materials LiFePO4。
The preparation of negative pole：
95g negative electrode active composition native graphites, 1.2gCMC, 2g conductive agent white carbon black are added in 120g deionized waters, so Afterwards stirring forms uniform in de-airing mixer, and being eventually adding 1.8gSBR carries out forming uniform negative pole after low rate mixing 30min Slurry.The cathode size is uniformly coated to into the both sides of the Copper Foil that thickness is 8 μm, then at 90 DEG C drying, roll-in, cut Prepared size is the negative pole of 500 × 44mm, wherein containing about 3.5g active component native graphites.
The assembling of battery
Above-mentioned positive pole, negative pole and polyethylene film are wound into respectively the pole piece of a square lithium ion battery, subsequently will LiPF6EC/EMC/DEC=1 is dissolved in by the concentration of 1mol/L:1:Nonaqueous electrolytic solution is formed in 1 mixed solvent, this is electrolysed During liquid is with the amount injection battery aluminum shell of 3.2g/Ah, sealing is respectively prepared lithium rechargeable battery A1-A3, B1.
(2) battery performance test
By lithium ion battery A1-A6 obtained in above-described embodiment 1-6 and lithium ion battery B1 batteries obtained in comparative example 1 It is individually placed in test cabinet, first constant-current constant-voltage charging is carried out with 1C in 25 DEG C of calorstats, charging upper limit is 3.65V；Shelve After 20min, 2.0V is discharged to from 3.65V with the electric current of 1C, records the discharge capacity first of battery, and calculated according to the following equation The specific discharge capacity of battery；
Specific discharge capacity=battery discharge capacity (mAh)/positive electrode weight (g) first
Lithium ion battery A1-A6 and B1 obtained above is individually placed in test cabinet to carry out with 1C in 25 DEG C of calorstats Charge-discharge test, voltage range 2.0V～3.65V, when circulation volume is less than 80% than the meansigma methodss of first three weeks capacity, record is followed The all numbers of ring.
The resultant battery performance of table 2
Data from table 2 can be seen that the LiFePO 4 material prepared using the method for the present invention as positive pole It is notable that active material prepares the initial discharge specific discharge capacity of positive pole and the battery A1-A6 being further assembled into, circulation cycle Higher than the reference cell B1 of comparative example 1, therefore, the LiFePO 4 material prepared using the method for the present invention is a kind of excellent performance Positive electrode active materials, not only manufacturing cost is remarkably decreased the method for the present invention, and equipment capacity is obviously improved, and using its as The chemical property of battery made by positive electrode active materials is also very excellent, and specific capacity is high, good cycle.
Applicant states that the present invention illustrates the method detailed of the present invention, but the present invention not office by above-described embodiment It is limited to above-mentioned method detailed, that is, does not mean that the present invention has to rely on above-mentioned method detailed and could implement.Art Technical staff it will be clearly understood that any improvement in the present invention, the equivalence replacement and auxiliary element to each raw material of product of the present invention Addition, selection of concrete mode etc., within the scope of all falling within protection scope of the present invention and disclosure.

Claims (10)

1. a kind of preparation method of LiFePO 4 material, it is characterised in that the method comprising the steps of：
(1) lithium source, source of iron, phosphorus source and optional doped chemical source are mixed to get into material, add carbon source and solvent to be ground, Then it is dried, obtains presoma；
(2) presoma that step (1) is obtained is crushed under conditions of auxiliary agent is added；
(3) crushing the material for obtaining to step (2) carries out briquetting, obtains the material after briquetting；
(4) material after the briquetting for obtaining step (3) is placed in reacting furnace, is heated up and constant temperature calcining under inert atmosphere, is broken It is broken, obtain LiFePO 4 material；
Wherein, the auxiliary agent is oxalic acid and/or ammonium oxalate.
2. method according to claim 1, it is characterised in that step (1) lithium source, source of iron, phosphorus source and optional mix Miscellaneous element source is according to elemental lithium:Ferrum element:P elements:The mol ratio (0.95～1.05) of doped chemical:(0.95～1.05): (0.95～1.05):(0～0.05) is mixed；
Preferably, step (1) lithium source includes lithium carbonate, Lithium hydrate, lithium dihydrogen phosphate, lithium nitrate, lithium oxalate, lithium acetate In Lithium Citrate de any one or at least two mixture；
Preferably, step (1) source of iron includes appointing in iron phosphate, Ferrox., iron acetate, iron sesquioxide or ferric nitrate Meaning it is a kind of or at least two mixture；
Preferably, step (1) phosphorus source includes phosphoric acid, ammonium dihydrogen phosphate, diammonium phosphate, ammonium phosphate, iron phosphate or phosphoric acid In dihydro lithium any one or at least two mixture；
Preferably, step (1) the doped chemical source include zinc source, manganese source, Tong Yuan, magnesium source, titanium source, zirconium source, silicon source, vanadium source, In chromium source, niobium source any one or at least two combination.
3. method according to claim 1 and 2, it is characterised in that step (1) carbon source includes glucose, sucrose, lemon In lemon acid, Polyethylene Glycol, polyvinyl alcohol, starch or cyclodextrin any one or at least two mixture；
Preferably, with the gross mass of step (1) material as 100% meter, the mass percent of step (1) carbon source is 1%～20%；
Preferably, step (1) solvent is selected from any one in water, methanol, ethanol, acetone or isopropanol or at least two Mixture；
Preferably, with the gross mass of step (1) material as 100% meter, the mass percent of step (1) solvent is 40%～50%；
Preferably, the mode of step (1) the addition carbon source and solvent is：It is initially charged after carbon source and adds solvent.
4. the method according to any one of claim 1-3, it is characterised in that step (1) is described grind the mode that adopts for Ball milling, the time of the ball milling is 3h～5h；
Preferably, the mode that step (1) drying is adopted is spray drying；
Preferably, the device for adopting that is spray-dried is for enclosed spray dryer；
Preferably, when being spray-dried, the temperature of air inlet is 220 DEG C～280 DEG C；
Preferably, when being spray-dried, the temperature of air outlet is 70 DEG C～90 DEG C.
5. the method according to any one of claim 1-4, it is characterised in that the addition of step (2) auxiliary agent is institute State the 1%～10% of forerunner's weight；
Preferably, the described crushing of step (2) is comminution by gas stream；
Preferably, step (2) device for adopting of crushing is for jet mill；
Preferably, step (2) D50 for being crushed to the material for obtaining is 1 μm～6 μm.
6. the method according to any one of claim 1-5, it is characterised in that the device that step (3) briquetting is adopted for Isostatic pressing machine；
Preferably, pressure during step (3) briquetting is 200MPa～300MPa.
7. the method according to any one of claim 1-6, it is characterised in that step (4) inert atmosphere is nitrogen gas In atmosphere, helium atmosphere, neon atmosphere, argon gas atmosphere, Krypton atmosphere, xenon atmosphere or carbon dioxide atmosphere any one or extremely The combination of few two kinds of atmosphere；
Preferably, the speed of step (4) intensification is 2 DEG C/min～20 DEG C/min；
Preferably, the temperature of step (4) constant temperature calcining is 600 DEG C～750 DEG C；
Preferably, the time of step (4) constant temperature calcining is 2h～6h；
Preferably, step (4) the broken device for adopting is for jaw crusher.
8. the LiFePO 4 material for being prepared using such as claim 1-7 any one methods described.
9. a kind of positive pole, it is characterised in that comprising the LiFePO 4 material described in claim 8 in the raw material components of the positive pole As positive electrode active materials.
10. a kind of lithium ion battery, it is characterised in that the lithium ion battery includes the LiFePO4 material described in claim 8 Material.
CN201611219247.8A 2016-12-26 2016-12-26 Low-cost lithium iron phosphate material, and preparation method and application thereof Pending CN106602060A (en)

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CN108996484A (en) * 2018-07-24 2018-12-14 深圳市德方纳米科技股份有限公司 The preparation method of the recoverying and utilizing method of waste lithium iron phosphate battery, iron manganese phosphate for lithium and lithium iron phosphate positive material
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CN109231182A (en) * 2018-08-28 2019-01-18 深圳市德方纳米科技股份有限公司 The method of ammonium dihydrogen phosphate, the preparation method of iron manganese phosphate for lithium and lithium iron phosphate positive material are prepared by phosphorus ore
CN109346789A (en) * 2018-08-30 2019-02-15 国网河南省电力公司电力科学研究院 A kind of recycling and regeneration process of lithium iron phosphate cathode material and regeneration cathode material
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CN110277542A (en) * 2018-03-16 2019-09-24 中天新兴材料有限公司 Lithium iron phosphate positive material and preparation method
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CN110620217A (en) * 2019-06-28 2019-12-27 湖北虹润高科新材料有限公司 Zinc-doped lithium iron phosphate/carbon composite material and preparation method thereof
CN111217347A (en) * 2018-11-23 2020-06-02 深圳市贝特瑞纳米科技有限公司 High-compaction lithium iron phosphate material and preparation method thereof
CN113745503A (en) * 2021-08-04 2021-12-03 北京泰丰先行新能源科技有限公司 Preparation method of high-compaction lithium iron phosphate cathode material
CN116964765A (en) * 2023-05-25 2023-10-27 广东邦普循环科技有限公司 Lithium iron phosphate positive electrode material, and preparation method and application thereof
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CN107814372A (en) * 2017-11-02 2018-03-20 沈阳国科金能新材料有限公司 A kind of preparation method and application of lithium iron phosphate positive material
CN108110241A (en) * 2017-12-18 2018-06-01 贝特瑞（天津）纳米材料制造有限公司 A kind of classification carbon modification NaTi2(PO4)3The Preparation method and use of negative material
CN110277542A (en) * 2018-03-16 2019-09-24 中天新兴材料有限公司 Lithium iron phosphate positive material and preparation method
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CN109346789A (en) * 2018-08-30 2019-02-15 国网河南省电力公司电力科学研究院 A kind of recycling and regeneration process of lithium iron phosphate cathode material and regeneration cathode material
CN109081322A (en) * 2018-11-12 2018-12-25 渤海大学 A kind of method that ihleite method extracts iron standby LiFePO4 in lateritic nickel ore
CN111217347A (en) * 2018-11-23 2020-06-02 深圳市贝特瑞纳米科技有限公司 High-compaction lithium iron phosphate material and preparation method thereof
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