CN101172599A - Process for producing carbon coated iron lithium phosphate - Google Patents
Process for producing carbon coated iron lithium phosphate Download PDFInfo
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- CN101172599A CN101172599A CNA2007101568197A CN200710156819A CN101172599A CN 101172599 A CN101172599 A CN 101172599A CN A2007101568197 A CNA2007101568197 A CN A2007101568197A CN 200710156819 A CN200710156819 A CN 200710156819A CN 101172599 A CN101172599 A CN 101172599A
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Abstract
The invention relates to a preparation method of lithium iron phosphate for the carbon cladding of a lithium ion battery. The prior lithium iron phosphate preparation technical art is complex, and has high cost. The invention has the synthetic process that: ferric oxide, phosphoric acid, simple organics and doped element compound are mixed and dried, the mol ratio of phosphate radical ion, ferric ion and doped element ion is 1:y:z, wherein, y is larger than or equal to 0.95 and smaller than or equal to 1, and y plus z is equal to 1; the mixture is added with lithium source compound, added with water to be mixed and dried, the mol ratio of lithium ion and phosphate radical ion is x:1, and x is larger than or equal to 0.95 and smaller than or equal to 1.05; the mixture which reacts for 2 to 20 hours under 500 to 800 DEG C is cooled in a furnace. The invention finally produces the precursor uniformly mixed with superfine crystal grain, and during the subsequent high temperature solid phase reaction, the end product lithium iron phosphate can be produced through shorter distance diffuseness of atoms. The end product has high purity, the crystallisation is good, the capacity is high, and the cycle stability is good.
Description
Technical field
The invention belongs to the energy and material technical field, particularly relate to the method preparing phosphate iron lithium that a kind of carbon that is used for lithium ion battery coats.
Technical background
Lithium ion battery is a kind of superior battery system.Characteristics such as it has the energy density height, and memory-less effect, pollution-free, life-span are long.Along with the lithium ion battery development of technology, it also has safe, can make the characteristics of arbitrary shape, is a kind of ideal energy storage device.
The lithium ion battery quilt widely should be in making various electronicss, as notebook computer, battery of mobile phone, digital camera, portable lighting equipment etc.Simultaneously, it also is used to power tool, electric bicycle and electromobile.Along with the consumption gradually of world petroleum resource, and the society requirement on environmental protection is improved gradually, power truck has obtained unprecedented opportunity to develop.As electric vehicle power sources, is the direction of power truck development with lithium ion battery.
In lithium ion battery, positive electrode material occupies important status, also is the emphasis of current lithium ion battery development.Traditional positive electrode material is a cobalt acid lithium, and its advantage is that energy height, good cycle, preparation are simple, technology maturation, Technological adaptability are good, and shortcoming is that price is too high, poor safety performance.The lithium manganate low price, but cycle performance and high-temperature behavior have much room for improvement./ 3rd materials that partly substitute cobalt with manganese and nickel are materials of acid energy of lithium manganate and cobalt and price compromise, and its cobalt contents can not fall very lowly, and the price of nickel is also very high, so its cost performance is undesirable.And the iron lithium phosphate cost is low, aboundresources, good cycle, is the ideal anode material for lithium-ion batteries.
In the existing iron lithium phosphate technology of preparing, the divalence source of iron (is the application for a patent for invention of 200510132430.X and 200510031116.2 as number of patent application) of employing is arranged, the employing ferric iron source is also arranged.The divalence source of iron need take measures to prevent its oxidation, so cost is higher in raw material production, storage, transportation.In ferric iron source, ferric oxide is a desirable feedstock, because it does not introduce impurity, and wide material sources, preparation process is simple, technical maturity, so price is very low.And picture ferric sulfate, iron(ic) chloride (be as the patent No. 200410103485.3 patent of invention) wait and can introduce impurity, in preparing the iron lithium phosphate process, need remove sulfate ion and chlorion.When tertiary iron phosphate during as source of iron (be as number of patent application 200510111791.6 patent application), though can not introduce impurity, tertiary iron phosphate preparation technology is comparatively complicated, and cost is higher.Other ferric iron source such as iron nitrate (be as the patent No. 200510000167.9 patent of invention), though also do not introduce impurity, its preparation cost is equally very high to contain ferric organism (be as number of patent application 200510111791.6 patent application).
The stable performance of ferric oxide, industrialized ferric oxide feed particles is bigger, and as carry out solid state sintering after simple the mixing, atom need could generate iron lithium phosphate fully through long distance diffusion.In this case, even through long-time insulation, raw material can not generate iron lithium phosphate fully.For with the ferric oxide refinement, need the long-time ball milling of high-octane ball-grinding machine, greatly to equipment requirements height, energy consumption height, dry sound.And the high-energy ball-grinding machine is when inventory increases, and efficient sharply reduces, and suitability for industrialized production is difficult to realize.
Summary of the invention
The purpose of this invention is to provide a kind of method for preparing the iron lithium phosphate of carbon coating, this method technological process is simple, equipment requirements is low, preparation cost is low.
The iron lithium phosphate that carbon coats among the present invention is expressed as Li
xFe
yM
zPO
4/ C.0.95≤x≤1.05 wherein, y+z=1,0.95≤y≤1.M is a kind of or wherein several mixture among Cr, Ni, Co and the Mn.
The present invention is a raw material with ferric oxide, phosphoric acid, Li source compound, simple organic and doping element compound, and its building-up process is:
1) ferric oxide, phosphoric acid, simple organic and doping element compound are mixed, 80～160 ℃ of oven dry down.Wherein, phosphate anion, iron ion and doped element ionic mol ratio are 1: y: z.
2) in the mixture of step 1), add Li source compound, add water and mix, 50～160 ℃ of oven dry down.Wherein the mol ratio of lithium ion and phosphate anion is x: 1.
3) with step 2) mixture place the atmosphere protection stove, in the reaction 2～20 hours down of 500～800 ℃ of high temperature, cool to 0～200 ℃ then with the furnace, generate the iron lithium phosphate that carbon coats.
Simple organic described in the step 1) is any one or the wherein multiple mixture in glucose, sucrose, dextrin and the starch.
The quality of the simple organic described in the step 1) is 10～40% of a ferric oxide quality.
Step 2) Li source compound described in is one or both the mixture in lithium hydroxide and the Quilonum Retard.
Step 2) doping element compound described in is carbonate, phosphoric acid salt, nitrate or the oxide compound of Cr, Ni, Co and Mn.
The present invention utilizes organism at high temperature to decompose, and produces reducing atmosphere, and Fe and doped element are reduced to+divalent.The product that organism decomposes, a part are used to reduce Fe and doped element, and a part is overflowed outside the stove, and remainder finally generates simple substance C, is coated on the iron lithium phosphate surface, forms the iron lithium phosphate that carbon coats.
Among the present invention, at high temperature, the reducing gas that organism decomposes can exhaust the oxygen in the atmosphere protection stove, and keeps the reductibility of furnace atmosphere, so at high temperature ,+divalent Fe and doped element can be not oxidized.The atmosphere protection stove adopts existing matured product on the market.
The specific conductivity of iron lithium phosphate own is very low, so the method that adopts C to coat forms the C film at grain surface, constitutes conductive network, increases total cubic conductance of material.Adopt transition element dopedly, can increase the specific conductivity of crystal grain inside, thereby further increase conductivity of electrolyte materials.
Among the present invention, ferric oxide in drying course, can decompose under organism and phosphatizing.After Li source compound adds, take place again to decompose once more, finally generate the presoma that crystal grain is superfine, mix.In follow-up high temperature solid state reaction, because presoma crystal grain is superfine, and mixes, atom is through generating the final product iron lithium phosphate than the short range diffusion.Therefore, final product purity height, complete crystallization, capacity height, good cycling stability.
The testing method of iron lithium phosphate is: with iron lithium phosphate, PVDF and the acetylene black mixed by 85: 5: 10, add NMP, stir and make slurry.Slurry is applied on the aluminium flake, 80 ℃ of oven dry down, as positive pole.With the lithium sheet is counter electrode (negative pole), and the employing porous polypropylene film is a barrier film, and its thickness is 20 μ m, porosity 60%, the about 30 μ m in aperture.Adopt LiPF
6Organic solvent solution be electrolytic solution.Organic solvent is DMC: EC=1: 1.Positive pole, barrier film, negative pole are washed into suitable diameter, fold by the order of positive pole, barrier film, negative pole and put into CR2025 button cell shell, inject electrolytic solution, then with cell sealing.Battery is carried out the charge-discharge performance test.Adopt first constant current again the mode of constant voltage charge, the charging stopping potential is 4.2V, adopts constant-current discharge, stopping potential is 2V.Electric current is exactly a capacity to the integration of time.
Embodiment
Embodiment one:
Phosphoric acid, ferric oxide and glucose are mixed, 80 ℃ of oven dry down.Wherein the mol ratio of Fe and P is 1: 1, and the quality of glucose is 10% of a ferric oxide quality.Add lithium hydroxide, add water and mix, wherein the ratio of Li and P is 1: 1.Under 160 ℃,, product is transferred in the atmosphere protection stove the product oven dry.Be incubated 20 hours down at 500 ℃, cool to 200 ℃ then with the furnace.The capacity that records its 1C is 130mAh/g, does not have decay substantially through 50 circle circulation volumes.
Embodiment two:
Phosphoric acid, ferric oxide, manganous carbonate and sucrose are mixed, 160 ℃ of oven dry down.Wherein the mol ratio of Fe, Mn and P is 0.95: 0.05: 1, and the quality of sucrose is 15% of a ferric oxide quality.Add Quilonum Retard, add water and mix, wherein the ratio of Li and P is 0.95: 1.Under 100 ℃,, product is transferred in the atmosphere protection stove the product oven dry.Be incubated 10 hours down at 600 ℃, cool to 150 ℃ then with the furnace.The capacity that records its 1C is 129mAh/g, does not have decay substantially through 50 circle circulation volumes.
Embodiment three:
Phosphoric acid, ferric oxide, nickelous nitrate and starch are mixed, 100 ℃ of oven dry down.Wherein the mol ratio of Fe, Ni and P is 0.98: 0.02: 1, and the quality of starch is 20% of a ferric oxide quality.The mixture that adds lithium hydroxide and Quilonum Retard adds water and mixes, and wherein the ratio of Li and P is 1.05: 1, and the mol ratio of lithium hydroxide and Quilonum Retard is 2: 1.Under 80 ℃,, product is transferred in the atmosphere protection stove the product oven dry.Be incubated 5 hours down at 700 ℃, cool to 100 ℃ then with the furnace.The capacity that records its 1C is 127mAh/g, does not have decay substantially through 50 circle circulation volumes.
Embodiment four:
Phosphoric acid, ferric oxide, Plessy's green and dextrin are mixed, 120 ℃ of oven dry down.Wherein the mol ratio of Fe, Cr and P is 0.99: 0.01: 1, and the quality of dextrin is 30% of a ferric oxide quality.Add lithium hydroxide, add water and mix, wherein the ratio of Li and P is 1.05: 1.Under 50 ℃,, product is transferred in the atmosphere protection stove the product oven dry.Be incubated 2 hours down at 800 ℃, cool to 50 ℃ then with the furnace.The capacity that records its 1C is 129mAh/g, does not have decay substantially through 50 circle circulation volumes.
Embodiment five:
Phosphoric acid, ferric oxide, cobalt sesquioxide and simple organic are mixed, 120 ℃ of oven dry down.Wherein the mol ratio of Fe, Cr and P is 0.99: 0.01: 1, and simple organic is the mixture of dextrose plus saccharose, and its total mass is 40% of a ferric oxide quality, and the mass ratio of dextrose plus saccharose is 1: 1.Add lithium hydroxide, add water and mix, wherein the ratio of Li and P is 1.05: 1.Under 50 ℃,, product is transferred in the atmosphere protection stove the product oven dry.Be incubated 7 hours down at 700 ℃, cool to 0 ℃ then with the furnace.The capacity that records its 1C is 128mAh/g, does not have decay substantially through 50 circle circulation volumes.
Embodiment six:
Phosphoric acid, ferric oxide, Manganse Dioxide, cobaltous carbonate and simple organic are mixed, 1 20 ℃ of oven dry down.Wherein the molar ratio of Fe, Mn, Co and P is 0.98: 0.01: 0.01: 1, and simple organic is the mixture of glucose, sucrose and dextrin, and its total mass is 25% of a ferric oxide quality, and the mass ratio of glucose, sucrose and dextrin is 1: 1: 1.Add lithium hydroxide, add water and mix, wherein the ratio of Li and P is 1.05: 1.Under 50 ℃,, product is transferred in the atmosphere protection stove the product oven dry.Be incubated 7 hours down at 700 ℃, cool to 30 ℃ then with the furnace.The capacity that records its 1C is 128mAh/g, does not have decay substantially through 50 circle circulation volumes.
Claims (1)
1. the method preparing phosphate iron lithium that coats of a carbon is characterized in that this method is is raw material with ferric oxide, phosphoric acid, Li source compound, simple organic and doping element compound, and its preparation process is:
(1) ferric oxide, phosphoric acid, simple organic and doping element compound are mixed, 80～160 ℃ of oven dry down, wherein phosphate anion, iron ion and doped element ionic mol ratio are 1: y: z, 0.95≤y≤1, y+z=1;
(2) add Li source compound in the mixture of step (1), add water and mix, 50～160 ℃ of oven dry down, wherein the mol ratio of lithium ion and phosphate anion is x: 1,0.95≤x≤1.05;
(3) mixture with step (2) places the atmosphere protection stove, reacts 2～20 hours down at 500～800 ℃, cools to 0～200 ℃ then with the furnace, generates the iron lithium phosphate that carbon coats;
Simple organic described in the step (1) is any one or the wherein multiple mixture in glucose, sucrose, dextrin and the starch;
The quality of the simple organic described in the step (1) is 10～40% of a ferric oxide quality;
Li source compound described in the step (2) is one or both the mixture in lithium hydroxide and the Quilonum Retard;
Doping element compound described in the step (2) is carbonate, phosphoric acid salt, nitrate or the oxide compound of Cr, Ni, Co and Mn.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2007101568197A CN101172599A (en) | 2007-11-12 | 2007-11-12 | Process for producing carbon coated iron lithium phosphate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2007101568197A CN101172599A (en) | 2007-11-12 | 2007-11-12 | Process for producing carbon coated iron lithium phosphate |
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| CN101172599A true CN101172599A (en) | 2008-05-07 |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101330141B (en) * | 2008-07-18 | 2010-06-02 | 清华大学 | Method for preparing lithium ionic battery anode material spherical LiFePO4 /C |
| CN101794881A (en) * | 2010-03-22 | 2010-08-04 | 河南联合新能源有限公司 | Method for preparing anode material of lithium ion batteries by one-step microwave sintering |
| CN101388454B (en) * | 2008-10-23 | 2010-09-22 | 天津斯特兰能源科技有限公司 | Method for preparing carbon coated phosphates positive pole material by super critical fluid |
| WO2010148638A1 (en) | 2009-06-21 | 2010-12-29 | 海特电子集团有限公司 | Method for producing composite lithium iron phosphate material and composite lithium iron phosphate material produced thereby |
| CN102227023A (en) * | 2011-05-16 | 2011-10-26 | 李朝林 | Lithium iron phosphate precursor and preparing method thereof |
| CN102280638A (en) * | 2011-07-04 | 2011-12-14 | 南陵恒昌铜箔制造有限公司 | Vegetable protein carbon cladded nanometer lithium iron phosphate anode material and preparation method thereof |
| CN102311109A (en) * | 2011-09-07 | 2012-01-11 | 河南帝隆科技研发有限公司 | Method for preparing LiFePO4/C composite cathode material by continuous reaction |
| CN101645518B (en) * | 2008-08-04 | 2012-05-09 | 株式会社日立制作所 | Nonaqueous electrolyte secondary batteries |
| CN102569795A (en) * | 2012-01-02 | 2012-07-11 | 株洲泰和高科技有限公司 | Comprehensive modification method for synthesis of lithium iron phosphate |
| CN107528061A (en) * | 2017-09-11 | 2017-12-29 | 太仓天润新材料科技有限公司 | A kind of electronics new material with high heat stability performance |
| WO2023023894A1 (en) * | 2021-08-23 | 2023-03-02 | 宁德时代新能源科技股份有限公司 | Carbon-coated lithium iron phosphate positive electrode active material, method for preparing same, positive electrode pole piece comprising same, and lithium-ion battery |
-
2007
- 2007-11-12 CN CNA2007101568197A patent/CN101172599A/en active Pending
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101330141B (en) * | 2008-07-18 | 2010-06-02 | 清华大学 | Method for preparing lithium ionic battery anode material spherical LiFePO4 /C |
| CN101645518B (en) * | 2008-08-04 | 2012-05-09 | 株式会社日立制作所 | Nonaqueous electrolyte secondary batteries |
| CN101388454B (en) * | 2008-10-23 | 2010-09-22 | 天津斯特兰能源科技有限公司 | Method for preparing carbon coated phosphates positive pole material by super critical fluid |
| WO2010148638A1 (en) | 2009-06-21 | 2010-12-29 | 海特电子集团有限公司 | Method for producing composite lithium iron phosphate material and composite lithium iron phosphate material produced thereby |
| CN101794881A (en) * | 2010-03-22 | 2010-08-04 | 河南联合新能源有限公司 | Method for preparing anode material of lithium ion batteries by one-step microwave sintering |
| CN102227023A (en) * | 2011-05-16 | 2011-10-26 | 李朝林 | Lithium iron phosphate precursor and preparing method thereof |
| CN102280638A (en) * | 2011-07-04 | 2011-12-14 | 南陵恒昌铜箔制造有限公司 | Vegetable protein carbon cladded nanometer lithium iron phosphate anode material and preparation method thereof |
| CN102311109A (en) * | 2011-09-07 | 2012-01-11 | 河南帝隆科技研发有限公司 | Method for preparing LiFePO4/C composite cathode material by continuous reaction |
| CN102311109B (en) * | 2011-09-07 | 2013-07-24 | 河南帝隆科技发展有限公司 | Method for preparing LiFePO4/C composite cathode material by continuous reaction |
| CN102569795A (en) * | 2012-01-02 | 2012-07-11 | 株洲泰和高科技有限公司 | Comprehensive modification method for synthesis of lithium iron phosphate |
| CN107528061A (en) * | 2017-09-11 | 2017-12-29 | 太仓天润新材料科技有限公司 | A kind of electronics new material with high heat stability performance |
| WO2023023894A1 (en) * | 2021-08-23 | 2023-03-02 | 宁德时代新能源科技股份有限公司 | Carbon-coated lithium iron phosphate positive electrode active material, method for preparing same, positive electrode pole piece comprising same, and lithium-ion battery |
| US11721804B2 (en) | 2021-08-23 | 2023-08-08 | Contemporary Amperex Technology Co., Limited | Carbon-coated lithium iron phosphate positive active material, method for preparing same, positive electrode plate containing same, and lithium-ion battery |
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Open date: 20080507 |