CN103633323B - A kind of preparation method of ferrous lithium phosphate cathode active material and the ferrous lithium phosphate cathode active material of preparation thereof - Google Patents

A kind of preparation method of ferrous lithium phosphate cathode active material and the ferrous lithium phosphate cathode active material of preparation thereof Download PDF

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CN103633323B
CN103633323B CN201210309734.9A CN201210309734A CN103633323B CN 103633323 B CN103633323 B CN 103633323B CN 201210309734 A CN201210309734 A CN 201210309734A CN 103633323 B CN103633323 B CN 103633323B
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lithium
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iron
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CN103633323A (en
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李阳
曹文玉
覃广文
张文伟
连水平
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BYD Co Ltd
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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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • 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

Abstract

The invention provides a kind of ferrous lithium phosphate cathode active material and preparation method thereof.Its preparation method comprises, first phosphorus source, the first source of iron and cationic surfactant are contacted to obtain solution A with the first lithium source, second phosphorus source, the second source of iron and anion surfactant are contacted to obtain solution B with the second lithium source, solution A and solution B are reacted to obtain LiFePO 4 under HTHP, method is simple and easy to realize, the compacted density of obtained positive electrode active materials is high, specific capacity and volume energy higher.

Description

A kind of preparation method of ferrous lithium phosphate cathode active material and the ferrous lithium phosphate cathode active material of preparation thereof
Technical field
The present invention relates to technical field of lithium ion, more particularly, is the ferrous lithium phosphate cathode active material of preparation method about a kind of ferrous lithium phosphate cathode active material and preparation thereof.
Background technology
Lithium ion battery has been widely used in the fields such as mobile communication, notebook computer, video camera, camera, portable instrument as the chemical power source of height ratio capacity, the electric automobile that Ye Shi various countries are studied energetically, the supporting power supply of the first-selection of space power system, become the first-selection of fungible energy source.
LiFePO 4 (LiFePO 4) be the study hotspot of active substance of lithium ion battery anode.Primary Study shows, LiFePO 4concentrate LiCoO 2, LiNiO 2, LiMnO 4respective advantage Deng material: not containing precious metal, cheaper starting materials, resource extreme enrichment; Operating voltage moderate (3.4V); Platform identity is good, and voltage is steady, theoretical capacity large (170mAh/g); Stability Analysis of Structures, security performance good (oxygen and phosphorus, with strong covalent bond strong bonded, make material be difficult to analyse oxygen and decompose); High-temperature behavior and good cycle; Volume-diminished during charging, bulk effect when coordinating with carbon negative pole material is good; Good with most of electrolyte system compatibility, storge quality is good and nontoxic, can as real green energy resource.
Existing synthesizing lithium ferrous phosphate (LiFePO 4) method mainly contain: solid sintering technology, liquid phase oxidation reducing process and hydro thermal method, the LiFePO 4 that hydro thermal method is uniformly dispersed owing to relatively can synthesize, particle is controlled, becomes the focus of existing research.Existing water heat transfer LiFePO 4 (LiFePO 4) method mainly contain: first prepare lithium phosphate under (1) normal temperature, and then add copperas solution, last raised temperature to synthesis temperature, and at such a temperature after constant temperature a period of time, cooling, washing, filtration can obtain LiFePO4; (2) mixed with ferrous sulfate by phosphoric acid at normal temperatures completely, then mixed with it by lithium hydroxide solution, be warming up to assigned temperature after reacting completely, at such a temperature after constant temperature a period of time, cooling, washing, filtration can obtain LiFePO4.Also have and add surfactant when reacting, as quaternary cationic surfactant, APES class non-ionic surface active agent, cetyl trimethyl ammonia bromide or polyethylene glycol etc., obtained excellent electrochemical performance, even particle size distribution, particle diameter D50 is at 1.5 ~ 2 μm, thing phase purity reaches more than 99%, and the LiFePO4 that electron conduction is high overcomes LiFePO 4the problem that the electronic conductivity of this material is poor, but the compacted density of this material under the pressure of 4Mpa maintains between 1.9 ~ 2.1g/cc substantially, 155 ~ 160mAh/g is held in than filling capacity dimension, 153 ~ 158mAh/g is held in than putting capacity dimension, the compacted density of material is low, and specific capacity and volume energy are still undesirable.
Summary of the invention
The present invention in order to the compacted density of the ferrous lithium phosphate cathode active material overcoming existing water heat transfer low, specific capacity and the undesirable technical problem of volume energy, there is provided a kind of compacted density high, specific capacity and the higher ferrous lithium phosphate cathode active material of volume energy and preparation method thereof.
First object of the present invention is to provide a kind of preparation method of ferrous lithium phosphate cathode active material, the method comprises, first phosphorus source, the first source of iron and cationic surfactant are contacted to obtain solution A with the first lithium source, second phosphorus source, the second source of iron and anion surfactant are contacted to obtain solution B with the second lithium source, solution A and solution B are reacted to obtain LiFePO 4 under HTHP.
Second object of the present invention is to provide a kind of ferrous lithium phosphate cathode active material, is prepared by the preparation method of above-mentioned ferrous lithium phosphate cathode active material.
The present inventor surprisingly finds to adopt technical scheme of the present invention, the cationic surfactant with charging neutrality effect in a technical scheme and anionic surfactant can not be applied in a technical scheme, surprisingly obtain compacted density high, specific capacity and the higher ferrous lithium phosphate cathode active material of volume energy, inferring may because the first phosphorus source, first source of iron and the first lithium source react under the condition being added with surfactant in liquid phase, second phosphorus source, second source of iron and the second lithium source also react under the condition being added with surfactant in liquid phase, all can prepare pattern rule, the primary particle that particle diameter is desirable, ensure that the homogeneous of material and stability, and all there is a large amount of cations on the surface of each primary particle in solution A, in solution B, all there is a large amount of anion on the surface of each primary particle, when solution A and solution B mixing, the negative ions on its surface will attract each other because of the neutralization of electric charge, thus the primary particle in solution A and the primary particle in solution B are combined closely react, gap is not had when particle is connected with particle yet, well utilize two kinds of surfactants in the charging neutrality of zwitterion and charging neutrality process may generate a kind of thick thing, particle and particle can be linked together closely, after hydro-thermal reaction, washing etc. after filtration, not only primary particle is still clearly for the positive electrode active materials of preparation, that is: under certain condition the chemical property of material is not affected, and between particle, have obvious agglomeration, second particle is obvious, close contact between particle and particle, space between primary particle diminishes, tail off, the compacted density of material is high, specific capacity and the volume energy of battery are higher.
Accompanying drawing explanation
Fig. 1 is the field emission electron scanning mirror * 50000 times of the LiFePO4 that the embodiment of the present invention 1 obtains.
Fig. 2 is the field emission electron scanning mirror * 20000 times of the LiFePO4 that the embodiment of the present invention 1 obtains.
Fig. 3 is the field emission electron scanning mirror * 50000 times of the LiFePO4 that the embodiment of the present invention 2 obtains.
Fig. 4 is the field emission electron scanning mirror * 20000 times of the LiFePO4 that the embodiment of the present invention 2 obtains.
Fig. 5 is the field emission electron scanning mirror * 50000 times of the LiFePO4 that the embodiment of the present invention 3 obtains.
Fig. 6 is the field emission electron scanning mirror * 20000 times of the LiFePO4 that the embodiment of the present invention 3 obtains.
Fig. 7 is the field emission electron scanning mirror * 50000 times of the LiFePO4 that comparative example 1 of the present invention obtains.
Fig. 8 is the field emission electron scanning mirror * 20000 times of the LiFePO4 that comparative example 1 of the present invention obtains.
Fig. 9 is the field emission electron scanning mirror * 50000 times of the LiFePO4 that comparative example 2 of the present invention obtains.
Figure 10 is the field emission electron scanning mirror * 20000 times of the LiFePO4 that comparative example 2 of the present invention obtains.
Embodiment
In order to make technical problem solved by the invention, technical scheme and beneficial effect clearly understand, below in conjunction with embodiment, the present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to explain the present invention, be not intended to limit the present invention.
The invention provides a kind of preparation method of ferrous lithium phosphate cathode active material, the method comprises, first phosphorus source, the first source of iron and cationic surfactant are contacted to obtain solution A with the first lithium source, second phosphorus source, the second source of iron and anion surfactant are contacted to obtain solution B with the second lithium source, solution A and solution B are reacted to obtain LiFePO 4 under HTHP, can obtain that compacted density is high, specific capacity and the higher ferrous lithium phosphate cathode active material of volume energy.
Wherein, react under HTHP after LiFePO 4, can to purify out LiFePO 4 particle, such as can comprise and lowering the temperature, centrifugal, washing, filter, dry etc., method is conventionally known to one of skill in the art, do not repeating at this, through washing, dried LiFePO 4 particle directly can be used as positive electrode active materials, also can for positive electrode active materials after carbon coated, directly through washing, the dope that may generate containing anion surfactant and cationic surfactant reaction in dried LiFePO 4 particle, or be exposed to other materials etc. that after in air, dope reaction generates, the present invention can wait this material of removing preferably by sintering, when being prepared into lithium ferrous phosphate composite material after carbon coated for positive electrode active materials, the sintering of carbon coated also can remove this material, and when sintering due to the existence of this material, particle and particle close contact, further increase the compacted density of positive electrode active materials.
Preferably, the mol ratio of the cationic surfactant in solution A and the anion surfactant in solution B is 1:0.5-2.Better utilize cationic surfactant and anion surfactant further, can better neutralize, obtain suitable thick thing.
Wherein, solution A and solution B are two independently systems, the reaction in the reaction in the first phosphorus source, the first source of iron and the first lithium source and the second phosphorus source, the second source of iron and the second lithium source can be the same or different, namely the relation of the amount in the relation of the amount in the first phosphorus source, the first source of iron and the first lithium source and the second phosphorus source, the second source of iron and the second lithium source can be the same or different, the present invention is preferred, the mole in the first phosphorus source: the mole=1:0.5-2 in the second phosphorus source; The mole of described first source of iron: the mole=1:0.5-2 of the second source of iron; The mole in described first lithium source: the mole=1:0.5-2 in the second lithium source.In better situation, the relation of the amount in the relation of the first phosphorus source, the first source of iron and the amount in the first lithium source and the second phosphorus source, the second source of iron and the second lithium source is as far as possible consistent, the i.e. mole in preferred the first phosphorus source: the mole in the second phosphorus source is about 1:1, the mole of the first source of iron: the mole of the second source of iron is also about 1:1, the mole in the first lithium source: the mole in the second lithium source is also about 1:1, make system after solution A and solution B mixing evenly, optimize further the stability of material.
By regulating the first phosphorus source, the relation of amount in the first source of iron and the first lithium source can obtain different materials, and such as solution A system can contain ferrous phosphate and phosphoric acid hydrogen two lithium etc.; Equally also can obtain different materials by the relation of the amount in adjustment second phosphorus source, the second source of iron and the second lithium source, such as solution B system can contain ferrous phosphate and lithium phosphate etc.In solution A and solution B, except surfactant, other substance classes and amount can be the same or different, preferably, containing lithium phosphate, ferrous phosphate and phosphoric acid hydrogen two lithium in solution A; Containing lithium phosphate, ferrous phosphate and phosphoric acid hydrogen two lithium in solution B; Preferably, the mol ratio of the ferrous phosphate in solution A and the ferrous phosphate in solution B is 1:0.5-2.
Preferably, the temperature of HTHP is 160 ~ 220 ° of C, and pressure is 0.8-1.2Mpa, and the time of reaction is 5 ~ 30h, and further preferably, the temperature of HTHP is 180 ~ 220 ° of C, and pressure is 0.8-1Mpa, and the time of reaction is 5 ~ 10h.Solution A and solution B can be added in autoclave simultaneously, make it that hydro-thermal reaction occur.
Also can first by after the mixing of solution A and solution B again together with add in autoclave hydro-thermal reaction occur, preferably solution A and solution B are reacted under HTHP also comprise before LiFePO 4 solution A and solution B are mixed under 130 ~ 220 ° of C, preferred further solution A and solution B to be mixed under 130 ~ 150 ° of C, mixing can be carried out in the environment outside autoclave, also can carry out in autoclave.
Cationic surfactant the present invention do not limit, preferably, cationic surfactant be selected from softex kw, laurate quaternary ammonium salt, Gemini quaternary ammonium salt (Gemini quaternary ammonium salt) or double type benzimidazole one or more, be softex kw in better situation.It can be such as the softex kw that Tianjin great Mao chemical reagent factory is produced.
Preferably, the mass percentage of solution A cationic surfactant is 0.01wt% ~ 0.1wt%, is 0.05wt% in better situation.The cationic surfactant of 0.01wt% ~ 0.1wt% is added with in the reaction system in i.e. the first phosphorus source, the first source of iron and the first lithium source, the reaction system in the first phosphorus source, the first source of iron and the first lithium source can be optimized further, make the first phosphorus source, primary particle that the reaction in the first source of iron and the first lithium source generates evenly, pattern is more perfect, can have cationic surfactant preferably in the coated with uniform of each primary particle simultaneously.
Wherein, first phosphorus source, first source of iron and cationic surfactant contact with the first lithium source as making the first phosphorus source, first source of iron and cationic surfactant and the first lithium source react, for the known various way of contact of the present invention, be generally first by the solution mixing containing the first phosphorus source and the first source of iron, then cationic surfactant is added, finally adding the first lithium source makes it react, preferably the first phosphorus source, the temperature that first source of iron and cationic surfactant contact with the first lithium source is 20 ~ 120 ° of C, more preferably 100 ~ 120 ° of C, time is 0.5-5h, further optimization primary particle pattern, the connection of particle and particle when guarantee solution A and solution B hybrid reaction, ensure compacted density.
Anion surfactant the present invention do not limit, preferably, anion surfactant be selected from neopelex, lauryl sodium sulfate or DGE carboxylate one or more, be neopelex in better situation.The neopelex anion surfactant such as can produced for Tianjin Kermel Chemical Reagent Co., Ltd..
Preferably, in solution B, the mass percentage of anion surfactant is 0.01wt% ~ 0.1wt%, is 0.05wt% in better situation.。The anion surfactant of 0.01wt% ~ 0.1wt% is added with in the reaction system in i.e. the second phosphorus source, the second source of iron and the second lithium source, the reaction system in the second phosphorus source, the second source of iron and second people's lithium source can be optimized further, make the second phosphorus source, primary particle that the reaction in the second source of iron and the second lithium source generates evenly, pattern is more perfect, can have anion surfactant preferably in the coated with uniform of each primary particle simultaneously.
Wherein, second phosphorus source, second source of iron and anion surfactant contact with the second lithium source as making the second phosphorus source, second source of iron and anion surfactant and the second lithium source react, for the known various way of contact of the present invention, be generally first by the solution mixing containing the second phosphorus source and the second source of iron, then anion surfactant is added, finally adding the second lithium source makes it react, preferably, second phosphorus source, the temperature that second source of iron and anion surfactant contact with the second lithium source is 20 ~ 120 ° of C, more preferably 100 ~ 120 ° of C, time is 0.5-5h, further optimization primary particle pattern, the connection of particle and particle when guarantee solution A and solution B hybrid reaction, ensure compacted density.
Wherein, the first phosphorus source and the second phosphorus source can be the same or different, preferably, the first phosphorus source and the second phosphorus source independently be selected from ammonium phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, ferrous phosphate, ferric phosphate and lithium dihydrogen phosphate one or more.
Wherein, first source of iron and the second source of iron can be the same or different, first source of iron and the second source of iron can for all insoluble or be insoluble in the iron compound of water, the compound of preferred deironing lithium outward only containing one or more elements in carbon, hydrogen, oxygen, phosphorus, more preferably independently be selected from ferrous oxalate, ferrous acetate, frerrous chloride, ferrous sulfate, ferrous phosphate, ferrous oxide, di-iron trioxide, tri-iron tetroxide and ferric phosphate one or more.
Wherein, first lithium source and the second lithium source can be the same or different, first lithium source and the second lithium source can be selected from soluble in water, and the compound only containing one or more elements in carbon, hydrogen, oxygen except lithium, preferably, the first lithium source and the second lithium source independently be selected from lithium carbonate, lithium hydroxide, lithium oxalate, lithium acetate, lithium fluoride, lithium chloride, lithium bromide, lithium iodide and lithium dihydrogen phosphate one or more.
Wherein, first phosphorus source, the first source of iron and cationic surfactant and the first catalytic environment in lithium source are the aqueous solution, can be the aqueous solution by the first phosphorus source, the first source of iron and cationic surfactant and the first each material in lithium source, also can be add above-mentioned each material in water.Second phosphorus source, the second source of iron and anion surfactant and the second catalytic environment in lithium source are the aqueous solution, can be the aqueous solution by the second phosphorus source, the second source of iron and anion surfactant and the second each material in lithium source, also can be add above-mentioned each material in water.
Preferably, the mole of P atom in the first phosphorus source: the mole of Fe atom in the first source of iron: in the first lithium source mole=0.95 ~ 1.05:0.95 ~ 1.05:2.85 ~ 3.15 of Li atom.The mole of P atom in second phosphorus source: the mole of Fe atom in the second source of iron: in the second lithium source mole=0.95 ~ 1.05:0.95 ~ 1.05:2.85 ~ 3.15 of Li atom.The mole of P atom in first phosphorus source in better situation: the mole of Fe atom in the first source of iron: the mole of P atom in the mole of Li atom and the second phosphorus source in the first lithium source: the mole of Fe atom in the second source of iron: in the second lithium source, the mole of Li atom is 1:1:3.
When the first phosphorus source is identical with the second phosphorus source, first source of iron is identical with the second source of iron, the mole of P atom in and the first phosphorus source identical with the second lithium source, first lithium source: the mole of Fe atom in the first source of iron: the mole of Li atom and the mole of P atom in the second phosphorus source in the first lithium source: the mole of Fe atom in the second source of iron: when the mole of Li atom is identical in the second lithium source, concrete steps of the present invention can for be first mixed to get E by phosphorus source and source of iron, E is divided into two parts of E1 and E2, the lithium source F of stoichiometric proportion is divided into two parts of F1 and F2 in the ratio of E1 and E2, then by E1, cationic surfactant contacts to obtain solution A with F1, by E2, anion surfactant contacts to obtain solution B with F2, in above-mentioned, the amount that further preferred cationic surfactant adds in E1 with F1 system is identical with the amount that anion surfactant adds in E2 with F2 system, wherein, the ratio more preferably 1:0.5-2 of E1 and E2, be 1:1 in better situation, namely the electric charge of cationic surfactant and anion surfactant can better neutralize, produce more excellent dope, and solution A system and solution B system reacting phase with, solution A and solution B mixing after particle evenly, system is more excellent, the more perfect gapless of connection of particle and particle, optimize compacted density, the ratio improving material fills capacity, than putting capacity and stability etc.
Wherein, ferrous lithium phosphate cathode active material also can be metal-doped LiFePO 4; adopt method of the present invention to prepare metal-doped LiFePO 4 and also belong to the scope of protection of the invention; metal M source can add when preparing solution A and solution B, adds when also can react under solution A and solution B mixing HTHP.Preferably, the method comprises the first phosphorus source, the first source of iron, a M source and cationic surfactant is contacted to obtain solution A with the first lithium source, and the second phosphorus source, the second source of iron, the 2nd M source and anion surfactant are contacted to obtain solution B with the second lithium source; One or more in one M source and the 2nd M source nitrate being selected from metal M independently, the nitric acid oxonium salt of metal M and the oxide of metal M; Described M is selected from one or more in Mn, Co, Ni, Ca, Mg, Zn, Ti, Nb, Y, Mo, Cu, Au, Ga, Zr, V and Al, M is called as doped chemical, the ionic conductivity of LiFePO4 can be improved, thus improve the high rate during charging-discharging of the battery using LiFePO4 as positive active material.The mol ratio of preferred M:Fe is 1:200 to 1:4, more preferably 1:100 to 1:9.
Wherein, ferrous lithium phosphate cathode active material also can be the LiFePO 4 of carbon compound; the LiFePO 4 adopting method of the present invention to prepare carbon compound also belongs to the scope of protection of the invention; preferably; solution A is reacted under HTHP also comprise after LiFePO 4 and be separated to obtain LiFePO 4 particle with solution B; LiFePO 4 particle is mixed with carbon source, dry, sinter to obtain the LiFePO 4 of compound afterwards.Described carbon source additive can be selected from carbohydrate soluble in water, is preferably selected from the aqueous solution of one or more of sucrose, glucose, fructose, lactose and maltose.The various methods that described drying can use this area conventional are dry, such as dry or spraying dry under agitation.Drying under described stirring condition can be carried out at 70-100 DEG C, preferably carries out at 80-85 DEG C, and it is 150-300 DEG C that described spray-dired condition is preferably air inlet temperature, and atomizing pressure is 0.1-0.8 MPa.Described sintering can be inert gas atmosphere protection under one-stage sintering or double sintering.From the viewpoint of energy consumption, preferred one-stage sintering, energy consumption is little; Consider from the crystallization situation of gained LiFePO4, preferred bis sintering, the dephasign of crystallization is few.Constant temperature 4-12 hour after described one-stage sintering is preferably warming up to 650-750 DEG C with 1-10 DEG C/min.Constant temperature 5-8 hour, constant temperature 8-20 hour after then second segment sintering is warming up to 600-800 DEG C with 1-10 DEG C/min after the preferred first paragraph sintering of described double sintering is warming up to 300-500 DEG C with 1-10 DEG C/min.Described inert atmosphere refer to not with any one gas or the admixture of gas of reactant and product generation chemical reaction, as one or more in nitrogen and periodic table of elements zero group gas.This inert atmosphere can be static atmosphere, is preferably the flowing atmosphere that gas flow rate is 2-50 liter/min.
Invention also provides a kind of ferrous lithium phosphate cathode active material, this positive electrode active materials is prepared by the preparation method of above-mentioned ferrous lithium phosphate cathode active material.
Further specific descriptions will be done to the present invention below by specific embodiment.
Embodiment 1
This embodiment illustrates the preparation of ferrous lithium phosphate cathode active material provided by the invention.
Take 30mol ferrous sulfate heptahydrate (purity 100wt%), 30mol phosphoric acid (purity 85wt%), 0.075mol softex kw (Tianjin great Mao chemical reagent factory) and 40kg deionized water and mix to obtain mixed solution, take after 90mol monohydrate lithium hydroxide (purity 100wt%) and 30kg deionized water mix and add under 120 ° of C in above-mentioned mixed solution, after reaction 30min, obtain solution A.
Take 30mol ferrous sulfate heptahydrate (purity 100wt%), 30mol phosphoric acid (purity 85wt%), 0.075mol neopelex (Tianjin Kermel Chemical Reagent Co., Ltd.) and 40kg deionized water to mix, take after 90mol monohydrate lithium hydroxide (purity 100wt%) and 30kg deionized water mix and add under 120 ° of C in above-mentioned mixed solution, after reaction 30min, obtain solution B.
Solution A and solution B are joined in autoclave, constant temperature 10h under 180 ° of C, 0.8Mpa, rear cooling, washing simultaneously, filter, dry to obtain LiFePO 4.
Take 400g glucose, add 20kg water, stir after dissolving completely, add above-mentioned LiFePO 4 4kg wherein, after stirring, spraying dry, after put into the atmosphere furnace of 700 ° of C, nitrogen flow 50L/h, sintering 8h obtains lithium ferrous phosphate composite material sample S1.
The SSX-550 type ESEM adopting Japanese Shimadzu Corporation (Shimadzu) to produce records the SEM photo (amplifying 2000 times and 50000 times) of above-mentioned obtained lithium ferrous phosphate composite material sample S1 as depicted in figs. 1 and 2.As can be seen from the SEM photo of Fig. 1 and Fig. 2, have obvious agglomeration between particle, second particle is obvious, due to its comparatively significantly reason of reuniting, and close contact between particle and particle, thus the space between primary particle diminishes, and tails off; Improve the compacted density of material greatly; Although and as can be seen from the figure have obvious second particle, its primary particle still clearly, that is: does not affect the chemical property of material under certain condition.
Embodiment 2
This embodiment illustrates the preparation of ferrous lithium phosphate cathode active material provided by the invention.
Adopt the method identical with embodiment 1 to prepare positive electrode active materials S2, different cationic surfactants is laurate quaternary ammonium salt, and anion surfactant is DGE carboxylate.
The SSX-550 type ESEM adopting Japanese Shimadzu Corporation (Shimadzu) to produce records the SEM photo (amplifying 2000 times and 50000 times) of above-mentioned obtained lithium ferrous phosphate composite material sample S2 as shown in Figure 3 and Figure 4.As can be seen from the SEM photo of Fig. 3 and Fig. 4, have obvious agglomeration between particle, second particle is obvious, due to its comparatively significantly reason of reuniting, and close contact between particle and particle, thus the space between primary particle diminishes, and tails off; Improve the compacted density of material greatly; Although and as can be seen from the figure have obvious second particle, its primary particle still clearly, that is: does not affect the chemical property of material under certain condition.
Embodiment 3
This embodiment illustrates the preparation of ferrous lithium phosphate cathode active material provided by the invention.
Take 30mol ferrous sulfate heptahydrate (purity 100wt%), 30mol phosphoric acid (purity 85wt%), 0.075mol softex kw (Tianjin great Mao chemical reagent factory) and 40kg deionized water and mix to obtain mixed solution, take after 90mol monohydrate lithium hydroxide (purity 100wt%) and 30kg deionized water mix and add under 50 ° of C in above-mentioned mixed solution, after reaction 30min, obtain solution A.
Take 30mol ferrous sulfate heptahydrate (purity 100wt%), 30mol phosphoric acid (purity 85wt%), 0.075mol neopelex (Tianjin Kermel Chemical Reagent Co., Ltd.) and 40kg deionized water to mix, take after 90mol monohydrate lithium hydroxide (purity 100wt%) and 30kg deionized water mix and add under 50 ° of C in above-mentioned mixed solution, after reaction 30min, obtain solution B.
Solution A and solution B are joined in autoclave, constant temperature 10h under 180 ° of C, 0.8Mpa, rear cooling, washing simultaneously, filter, dry to obtain LiFePO 4.
Take 400g glucose, add 20kg water, stir after dissolving completely, add above-mentioned LiFePO 4 4kg wherein, after stirring, spraying dry, after put into the atmosphere furnace of 700 ° of C, nitrogen flow 50L/h, sintering 8h obtains lithium ferrous phosphate composite material sample S3.
The SSX-550 type ESEM adopting Japanese Shimadzu Corporation (Shimadzu) to produce records the SEM photo (amplifying 2000 times and 50000 times) of above-mentioned obtained lithium ferrous phosphate composite material sample S3 as shown in Figure 5 and Figure 6.As can be seen from the SEM photo of Fig. 5 and Fig. 6, have obvious agglomeration between particle, second particle is obvious, due to its comparatively significantly reason of reuniting, and close contact between particle and particle, thus the space between primary particle diminishes, and tails off; Improve the compacted density of material greatly; Although and as can be seen from the figure have obvious second particle, its primary particle still clearly, that is: does not affect the chemical property of material under certain condition.
Embodiment 4
This embodiment illustrates the preparation of ferrous lithium phosphate cathode active material provided by the invention.
Take 30mol ferrous sulfate heptahydrate (purity 100wt%), 30mol phosphoric acid (purity 85wt%), (Tianjin great Mao chemical reagent factory and 40kg deionized water mix to obtain mixed solution to 0.075mol softex kw, take after 90mol monohydrate lithium hydroxide (purity 100wt%) and 30kg deionized water mix and add under 100 ° of C in above-mentioned mixed solution, after reaction 30min, obtain solution A.
Take 30mol ferrous sulfate heptahydrate (purity 100wt%), 30mol phosphoric acid (purity 85wt%), 0.075mol neopelex (Tianjin Kermel Chemical Reagent Co., Ltd.) and 40kg deionized water to mix, take after 90mol monohydrate lithium hydroxide (purity 100wt%) and 30kg deionized water mix and add under 100 ° of C in above-mentioned mixed solution, after reaction 30min, obtain solution B.
Solution A and solution B are joined in autoclave, constant temperature 10h under 180 ° of C, 0.8Mpa, rear cooling, washing simultaneously, filter, dry to obtain LiFePO 4.
Take 400g glucose, add 20kg water, stir after dissolving completely, add above-mentioned LiFePO 4 4kg wherein, after stirring, spraying dry, after put into the atmosphere furnace of 700 ° of C, nitrogen flow 50L/h, sintering 8h obtains lithium ferrous phosphate composite material sample S4.
Embodiment 5
This embodiment illustrates the preparation of ferrous lithium phosphate cathode active material provided by the invention.
Take 30mol ferrous sulfate heptahydrate (purity 100wt%), 30mol phosphoric acid (purity 85wt%), 0.075mol softex kw (Tianjin great Mao chemical reagent factory) and 40kg deionized water and mix to obtain mixed solution, take after 90mol monohydrate lithium hydroxide (purity 100wt%) and 30kg deionized water mix and add under 50 ° of C in above-mentioned mixed solution, after reaction 30min, obtain solution A.
Take 30mol ferrous sulfate heptahydrate (purity 100wt%), 30mol phosphoric acid (purity 85wt%), 0.075mol neopelex (Tianjin Kermel Chemical Reagent Co., Ltd.) and 40kg deionized water to mix, take after 90mol monohydrate lithium hydroxide (purity 100wt%) and 30kg deionized water mix and add under 50 ° of C in above-mentioned mixed solution, after reaction 30min, obtain solution B.
Solution A and solution B are joined in autoclave, constant temperature 10h under 180 ° of C, 0.8Mpa, rear cooling, washing simultaneously, filter, dry to obtain LiFePO 4 S5.
Embodiment 6
This embodiment illustrates the preparation of ferrous lithium phosphate cathode active material provided by the invention.
Take 15mol ferrous sulfate heptahydrate (purity 100wt%), 15mol phosphoric acid (purity 85wt%), 0.038mol softex kw (Tianjin great Mao chemical reagent factory) and 20kg deionized water and mix to obtain mixed solution, take after 45mol monohydrate lithium hydroxide (purity 100wt%) and 15kg deionized water mix and add under 120 ° of C in above-mentioned mixed solution, after reaction 30min, obtain solution A.
Take 30mol ferrous sulfate heptahydrate (purity 100wt%), 30mol phosphoric acid (purity 85wt%), 0.075mol neopelex (Tianjin Kermel Chemical Reagent Co., Ltd.) and 40kg deionized water to mix, take after 90mol monohydrate lithium hydroxide (purity 100wt%) and 30kg deionized water mix and add under 120 ° of C in above-mentioned mixed solution, after reaction 30min, obtain solution B.
Solution A and solution B are joined in autoclave, constant temperature 10h under 180 ° of C, 0.8Mpa, rear cooling, washing simultaneously, filter, dry to obtain LiFePO 4.
Take 400g glucose, add 20kg water, stir after dissolving completely, add above-mentioned LiFePO 4 4kg wherein, after stirring, spraying dry, after put into the atmosphere furnace of 700 ° of C, nitrogen flow 50L/h, sintering 8h obtains lithium ferrous phosphate composite material sample S6.
Embodiment 7
This embodiment illustrates the preparation of ferrous lithium phosphate cathode active material provided by the invention.
Take 30mol ferrous sulfate heptahydrate (purity 100wt%), 30mol phosphoric acid (purity 85wt%), 0.075mol softex kw (Tianjin great Mao chemical reagent factory) and 40kg deionized water and mix to obtain mixed solution, take after 90mol monohydrate lithium hydroxide (purity 100wt%) and 30kg deionized water mix and add under 120 ° of C in above-mentioned mixed solution, after reaction 30min, obtain solution A.
Take 15mol ferrous sulfate heptahydrate (purity 100wt%), 15mol phosphoric acid (purity 85wt%), 0.038mol neopelex (Tianjin Kermel Chemical Reagent Co., Ltd.) and 20kg deionized water to mix, take after 45mol monohydrate lithium hydroxide (purity 100wt%) and 15kg deionized water mix and add under 120 ° of C in above-mentioned mixed solution, after reaction 30min, obtain solution B.
Solution A and solution B are joined in autoclave, constant temperature 10h under 180 ° of C, 0.8Mpa, rear cooling, washing simultaneously, filter, dry to obtain LiFePO 4.
Take 400g glucose, add 20kg water, stir after dissolving completely, add above-mentioned LiFePO 4 4kg wherein, after stirring, spraying dry, after put into the atmosphere furnace of 700 ° of C, nitrogen flow 50L/h, sintering 8h obtains lithium ferrous phosphate composite material sample S7.
Comparative example 1
This embodiment illustrates the preparation of existing ferrous lithium phosphate cathode active material.
Take 60mol ferrous sulfate heptahydrate (purity 100wt%), 60mol phosphoric acid (purity 85wt%), 0.15mol softex kw (Tianjin great Mao chemical reagent factory) and 80kg deionized water mix to obtain mixed solution, take after 180mol monohydrate lithium hydroxide (purity 100wt%) and 60kg deionized water mix and slowly join under 25 ° of C in above-mentioned mixed solution, flow control is 24L/h, after reaction 30min, join in autoclave, at 180 ° of C, constant temperature 10h under 0.8Mpa, rear cooling, washing, filter, dry to obtain LiFePO 4.
Take 400g glucose, add 20kg water, stir after dissolving completely, add above-mentioned LiFePO 4 4kg wherein, after stirring, spraying dry, after put into the atmosphere furnace of 700 ° of C, nitrogen flow 50L/h, sintering 8h obtains lithium ferrous phosphate composite material sample DS1.
The SSX-550 type ESEM adopting Japanese Shimadzu Corporation (Shimadzu) to produce records the SEM photo (amplifying 2000 times and 50000 times) of above-mentioned obtained lithium ferrous phosphate composite material sample DS1 as shown in Figure 7 and Figure 8.As can be seen from the SEM photo of Fig. 7 and Fig. 8, the material primary particle of preparation clearly, has larger space between particle and particle.
Comparative example 2
This embodiment illustrates the preparation of existing ferrous lithium phosphate cathode active material.
Take 60mol ferrous sulfate heptahydrate (purity 100wt%), 60mol phosphoric acid (purity 85wt%), 0.15mol neopelex (Tianjin Kermel Chemical Reagent Co., Ltd.) and 80kg deionized water mix to obtain mixed solution, take after 180mol monohydrate lithium hydroxide (purity 100wt%) and 60kg deionized water mix and slowly join under 25 ° of C in above-mentioned mixed solution, flow control is 24L/h, after reaction 30min, join in autoclave, at 180 ° of C, constant temperature 10h under 0.8Mpa, rear cooling, washing, filter, dry to obtain LiFePO 4.
Take 400g glucose, add 20kg water, stir after dissolving completely, add above-mentioned LiFePO 4 4kg wherein, after stirring, spraying dry, after put into the atmosphere furnace of 700 ° of C, nitrogen flow 50L/h, sintering 8h obtains lithium ferrous phosphate composite material sample DS2.
The SSX-550 type ESEM adopting Japanese Shimadzu Corporation (Shimadzu) to produce records the SEM photo (amplifying 2000 times and 50000 times) of above-mentioned obtained lithium ferrous phosphate composite material sample S2 as shown in Figure 9 and Figure 10.As can be seen from the SEM photo of Fig. 9 and Figure 10, the material primary particle of preparation clearly, has larger space between particle and particle.
Performance test
1, compacted density:
(1) grinding tool: external diameter 20mm, cylindrical 316 stainless steels of internal diameter 12mm, long 20mm, bottom fitting seal, upper end open; There are 316 stainless steel pressure rods of batching, diameter 11.5mm simultaneously;
(2) take positive electrode active materials sample S1-S7 and DS1-DS2 that mass M is the above-mentioned preparation of 1.0000g, be poured in above-mentioned grinding tool, constant voltage 30 seconds under the pressure of 4Mpa, take out, its thickness of miking L(mm); Formula p=1000/113.04L unit g/cm3.
2, battery performance
The preparation of battery:
(1) preparation of positive plate: get sample S1-S7 and DS1-DS2 of above-mentioned preparation as positive electrode active materials, be that 100:4:5 is dissolved in 1-METHYLPYRROLIDONE with acetylene black and PVDF with weight ratio respectively, be coated in after stirring on aluminium foil, baking, temperature is 100 ± 5 DEG C, use tablet press machine rolls, and rolling cut becomes positive plate, containing 10 grams of positive active materials on every sheet positive plate.
(2) preparation of negative plate: be that 100:3:6 is dissolved in 1-METHYLPYRROLIDONE with weight ratio by graphite, acetylene black and PVDF, be coated on Copper Foil after stirring, baking, temperature is 100 ± 5 DEG C, use tablet press machine rolls, and rolling cut becomes negative plate, containing 5 grams of graphite on every sheet negative plate.
(3) above-mentioned positive and negative electrode pole piece and 20 μm of thick polypropylene diaphragms are wound into rectangular lithium ion battery battery core, to be placed in battery case and to weld, subsequently, inject 1.0mol/LLiPF6/ (EC+EMC+DMC) (wherein EC, EMC and DMC mass ratio is 1:1:1) electrolyte, sealing, respectively obtained battery sample S11-S77 and DS11-DS22.
Specific capacity is tested: above-mentioned obtained battery sample S11-S77 and DS11-DS22 is at room temperature shelved 5min respectively, then with 0.8mA constant current charge, by voltage 3.8V, 3.8V constant voltage charge again, by electric current 0.1mA, shelves 5min, after with 0.8mA constant-current discharge, deboost 2.5V, the initial charge capacity of record battery and discharge capacity, and calculate the specific discharge capacity of battery according to the following equation; Mass ratio fills capacity=battery initial charge capacity (MAH)/positive electrode weight (gram); Mass ratio puts capacity=battery discharge capacity (MAH)/positive electrode weight (gram) first, and test result is as table 1.
Cycle performance is tested: by above-mentioned obtained battery sample S11-S77 and DS11-DS22 respectively at room temperature, first with 0.8mA constant current charge, deboost 3.8V, then 3.8V constant voltage charge, by electric current 0.1mA, shelve 5min, with 0.8mA constant-current discharge, record discharge capacity, repeat 500 postscript recording playback capacitances, calculate the capability retention after 500 times, discharge capacity (MAH)/discharge capacity first behind capability retention=500 time, the results are shown in Table 1.
table 1
The compacted density of positive electrode active materials prepared of the present invention is high as can be seen from Table 1, and the charge/discharge capacity of the battery prepared as positive electrode active materials with LiFePO 4 carbon composite of the present invention also improves.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any amendments done within the spirit and principles in the present invention, equivalent replacement and improvement etc., all should be included within protection scope of the present invention.

Claims (18)

1. the preparation method of a ferrous lithium phosphate cathode active material, it is characterized in that, the method comprises, first phosphorus source, the first source of iron and cationic surfactant are contacted to obtain solution A with the first lithium source, second phosphorus source, the second source of iron and anion surfactant are contacted to obtain solution B with the second lithium source, solution A and solution B are reacted to obtain LiFePO 4 under HTHP; The temperature of described HTHP is 160 ~ 220 ° of C, and pressure is 0.8-1.2MPa.
2. preparation method according to claim 1, is characterized in that, the mol ratio of the cationic surfactant in described solution A and the anion surfactant in solution B is 1:0.5-2.
3. preparation method according to claim 1, is characterized in that, the mole in described first phosphorus source: the mole=1:0.5-2 in the second phosphorus source; The mole of described first source of iron: the mole=1:0.5-2 of the second source of iron; The mole in described first lithium source: the mole=1:0.5-2 in the second lithium source.
4. preparation method according to claim 1, is characterized in that, containing lithium phosphate, ferrous phosphate and phosphoric acid hydrogen two lithium in described solution A; Containing lithium phosphate, ferrous phosphate and phosphoric acid hydrogen two lithium in described solution B; The mol ratio of the ferrous phosphate in described solution A and the ferrous phosphate in solution B is 1:0.5-2.
5. preparation method according to claim 1, is characterized in that, the time of reaction is 5 ~ 30h.
6. preparation method according to claim 1, is characterized in that, describedly solution A and solution B is reacted also comprise before LiFePO 4 and solution A and solution B being mixed under 130 ~ 220 ° of C under HTHP.
7. preparation method according to claim 1, is characterized in that, described cationic surfactant be selected from softex kw, laurate quaternary ammonium salt, Gemini quaternary ammonium salt or double type benzimidazole one or more.
8. preparation method according to claim 1, is characterized in that, the mass percentage of described solution A cationic surfactant is 0.01wt% ~ 0.1wt%.
9. preparation method according to claim 1, is characterized in that, the temperature that described first phosphorus source, the first source of iron and cationic surfactant contact with the first lithium source is 20 ~ 120 ° of C, and the time is 0.5-5h.
10. preparation method according to claim 1, is characterized in that, described anion surfactant be selected from neopelex, lauryl sodium sulfate or DGE carboxylate one or more.
11. preparation methods according to claim 1, is characterized in that, in described solution B, the mass percentage of anion surfactant is 0.01wt% ~ 0.1wt%.
12. preparation methods according to claim 1, is characterized in that, the temperature that described second phosphorus source, the second source of iron and anion surfactant contact with the second lithium source is 20 ~ 120 ° of C, and the time is 0.5-5h.
13. preparation methods according to claim 1, is characterized in that, described first phosphorus source and the second phosphorus source independently be selected from ammonium phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, ferrous phosphate, ferric phosphate and lithium dihydrogen phosphate one or more;
Described first source of iron and the second source of iron independently be selected from ferrous oxalate, ferrous acetate, frerrous chloride, ferrous sulfate, ferrous phosphate, ferrous oxide, di-iron trioxide, tri-iron tetroxide and ferric phosphate one or more;
Described first lithium source and the second lithium source independently be selected from lithium carbonate, lithium hydroxide, lithium oxalate, lithium acetate, lithium fluoride, lithium chloride, lithium bromide, lithium iodide and lithium dihydrogen phosphate one or more;
The mole of P atom in described first phosphorus source: the mole of Fe atom in the first source of iron: in the first lithium source mole=0.95 ~ 1.05:0.95 ~ 1.05:2.85 ~ 3.15 of Li atom;
The mole of P atom in described second phosphorus source: the mole of Fe atom in the second source of iron: in the second lithium source mole=0.95 ~ 1.05:0.95 ~ 1.05:2.85 ~ 3.15 of Li atom.
14. preparation methods according to claim 1, it is characterized in that, described method comprises phosphorus source and source of iron is mixed to get E, E is divided into two parts of E1 and E2, the lithium source F of stoichiometric proportion is divided into two parts of F1 and F2 in the ratio of E1 and E2, then E1, cationic surfactant and F1 are contacted to obtain solution A, E2, anion surfactant and F2 are contacted to obtain solution B, the molar ratio of E1 and E2 is 1:0.5-2.
15. preparation methods according to claim 1, it is characterized in that, described method comprises, first phosphorus source, the first source of iron, a M source and cationic surfactant are contacted to obtain solution A with the first lithium source, the second phosphorus source, the second source of iron, the 2nd M source and anion surfactant are contacted to obtain solution B with the second lithium source; One or more in one M source and the 2nd M source nitrate being selected from metal M independently, the nitric acid oxonium salt of metal M and the oxide of metal M; Described M is selected from one or more in Mn, Co, Ni, Ca, Mg, Zn, Ti, Nb, Y, Mo, Cu, Au, Ga, Zr, V and Al.
16. preparation methods according to claim 1, it is characterized in that, describedly solution A is reacted with solution B under HTHP also comprise after LiFePO 4 and be separated to obtain LiFePO 4 particle, LiFePO 4 particle is mixed with carbon source, drying, sinters to obtain the LiFePO 4 of compound afterwards.
17. preparation methods according to claim 16, is characterized in that, described carbon source is selected from the aqueous solution of one or more of sucrose, glucose, fructose, lactose or maltose; Described drying is spraying dry; Described spray-dired air inlet temperature is 150-300 DEG C, and atomizing pressure is 0.1-0.8Mpa; The method of described sintering sinters 4-12h in 650-750 ° of C under being included in inert gas atmosphere protection.
18. 1 kinds of ferrous lithium phosphate cathode active materials, is characterized in that, this positive electrode active materials is prepared by the preparation method of the ferrous lithium phosphate cathode active material described in claim 1-17 any one.
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