CN102219200A - Method for synthesizing cathode material LiFexM1-xPO4 of lithium ion battery - Google Patents

Method for synthesizing cathode material LiFexM1-xPO4 of lithium ion battery Download PDF

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CN102219200A
CN102219200A CN2011100733846A CN201110073384A CN102219200A CN 102219200 A CN102219200 A CN 102219200A CN 2011100733846 A CN2011100733846 A CN 2011100733846A CN 201110073384 A CN201110073384 A CN 201110073384A CN 102219200 A CN102219200 A CN 102219200A
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cathode material
lithium ion
compound
ion battery
battery life
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骆宏钧
郭军
蒋华锋
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JIANGSU GUOTAI LIBAO NEW MATERIAL CO Ltd
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JIANGSU GUOTAI LIBAO NEW MATERIAL CO Ltd
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • 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
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Abstract

The invention reveals a method for synthesizing a cathode material LiFexM1-xPO4 of a lithium ion battery, the M is one or more selected from metal elements of Mn, Fe, Ni, Co, Al, Mg, Ti and Cu; 0<=x<=1, the method comprises the following steps: (a) preparing raw materials; (b) preparing a precursor; (c) preparing an oxide; (d) preparing the cathode material. The invention has the advantages of low cost, energy saving and high efficiency, easy to control and low pollution.

Description

Cathode material for lithium ion battery LiFe xM 1-xPO 4Synthetic method
Technical field
The present invention relates to a kind of cathode material for lithium ion battery LiFe xM 1-xPO 4The preparation method, belong to electrochemical field.
Background technology
Continually developing of new forms of energy is the important foundation of human social, and along with the progress of science and technology, people are to being that the demand of the removable energy of carrier is more and more strong with the battery.Lithium dynamical battery can be widely used on various power tools, electric vehicle and the energy storage device.Development lithium dynamical battery industry substitutes oil with electric power, meets the national energy strategy, meets environmental protection requirement, the economical, societal benefits of containing unlimited development space and being difficult to estimate with numeral.
LiFe xM 1-xPO 4Be to be hopeful the positive electrode material of high volume applications at present most in lithium-ion-power cell.The ball-type active material has higher energy density and cycle performance with its lithium ion battery that makes owing to have higher tap density, thus ball-typeization oneself become the important development direction of battery material.
At present only mainly contain two kinds of coprecipitation method (or crystallization control method) and spray-drying processes than ball-type cathode material.Examine elder generations such as grinding the Lei Min of institute as Tsing-Hua University and synthesize the ball-type tertiary iron phosphate with coprecipitation method, be that the raw material sintering obtains spherical LiFePO 4 (power technology 130 (1): 112006), Jiangsu University is sternly red, Zhou Jianxin etc. also made spherical LiFePO 4 (process engineering journal 8 (5): 9832008) with this method with it then.Use when this method is produced and exist utilization rate of raw materials low, speed of response reaches difficult problems such as wastewater treatment slowly.
Physics and chemistry institute of the Chinese Academy of Sciences is in cutting edge of a knife or a sword, and Zhang Jingjie etc. are carbon source with the carbon black, adopts spraying drying-carbothermic method (SDCTM) to prepare the spherical LiFePO in porous crack 4(battery industry 13 (6): 52008), University Of Tianjin soars/C positive electrode material, and Tang Zhiyuan etc. have also prepared spherical LiFePO 4 with this method.Use when this method is produced and exist the cycle long, the energy consumption height, therefore a series of difficult problems such as solvent recuperation are not applied in the suitability for industrialized production of cathode material for lithium ion battery so far yet.
The powder by atomization technology is mainly used in NiMnCo at present, the preparation of catalytic alloy powder such as FeNi, during production starting material are joined after according to target each constituent content of product prepares in the intermediate frequency furnace successively and be infused in the enclosed system after the energising heating and melting, and simultaneously atomizing mediums such as water, gas are flowed in molten metal bath by the special nozzle jetting action, this metal liquid stream is torn and disperses also to be frozen into rapidly spherical granules, collects and obtains product.
Summary of the invention
Defective in view of above-mentioned prior art exists the objective of the invention is to propose a kind of efficient energy-saving, controls cathode material for lithium ion battery LiFe easily xM 1-xPO 4The preparation method.
Purpose of the present invention will be achieved by the following technical programs:
A kind of cathode material for lithium ion battery LiFe xM 1-xPO 4Synthetic method, described M is selected from one or more among metallic element Mn, Fe, Ni, Co, Al, Mg, Ti and the Cu; 0≤x≤1 comprises the steps:
(a) starting material configuration: according to target the content of each metallic element of product obtains raw material with raw material metal or its oxide compound by the suitable proportion collocation;
(b) presoma preparation: above-mentioned raw materials is heated to 1000 ℃～1800 ℃ by energising in the suitable order adding intermediate frequency furnace, after melting fully, it injects atomisation unit, pressure and flow by the control atomizing medium make submicron order ball-type composite metal powder, be presoma, described atomizing medium comprises water and/or gas;
(c) oxide compound preparation: sintering in the oxidizing atmosphere of the above-mentioned presoma that obtains in 200 ℃～700 ℃ temperature ranges is obtained oxide compound Fe xM yO z, 0≤x, y≤2,1≤z≤4;
(d) cathode material preparation: the oxide compound that above-mentioned reaction is obtained mixes an amount of lithium-containing compound, P contained compound and reductibility compound and obtained cathode material for lithium ion battery LiFe in once sintered at least 2～40 hours in 400 ℃～1000 ℃, inert atmosphere protection xM 1-xPO 4, 0≤x≤1.
Further, lithium-containing compound is selected from Li described in the step (d) 2CO 3, LiOH, LiF, LiH 2PO 4And Li 3PO 4In one or more, the add-on of described lithium-containing compound is n in molar ratio Li: n (Fe+M)=0.9～1.1: 1.
Further, P contained compound is selected from NH described in the step (d) 4H 2PO 4, (NH 4) 2HPO 4, LiH 2PO 4, Li 2HPO 4, Li 3PO 4, FePO 4And AlPO 4In one or more, the add-on of described P contained compound is n in molar ratio (Fe+M): n P=0.9～1.1: 1.
Further, reductibility compound described in the step (d) is selected from one or more in carbon, acetylene black, sucrose and the polyvinyl alcohol.
Compared with prior art, beneficial effect of the present invention is: (1) clean and effective, utilization rate of raw materials can reach more than 99.5%.And conventional coprecipitation method is because the complexing action of complexing agent (generally using ammoniacal liquor) and the influence of sedimentable matter solubleness cause utilization rate of raw materials generally in 95%, a large amount of noble metal enters filtrate with the ionic form and is difficult to recycle during production, this has not only increased cost, has also polluted human physical environment of depending on for existence.And the use of a large amount of ammoniacal liquor makes that also production environment is relatively poor in the reaction process.(2) the big panel height of throughput, at present use oxyhydroxide or carbonate etc. to be precipitation agent, ammoniacal liquor etc. are that the coprecipitation method cathode material preparation technology of complexing agent need pass through co-precipitation, a plurality of links such as ageing, complex process, 24 hours consuming time or longer, and use the powder by atomization technology with one spray of starting material fusing back, convenient and swift, can finish the production of precursor half an hour.(3) excellent performance: a, tap density height, the precursor material tap density that coprecipitation method makes is generally at 1.0g/cm 3Below, and powder particle is difficult to reach the ball-type effect; Though spray drying method for preparation also can prepare spheroidal particle, energy consumption is big, and efficient is low, and the more form with hollow ball exists.The powder by atomization technology can simply realize the powdered material ball-typeization, product tap density 1.8g/cm 3More than.B, doping conveniently only need this metal simple-substance or oxide compound etc. are melted the doping effect that just can realize that dispersion effect is high simultaneously as starting material when needing to mix other metals, so atomization are more suitable for being used as the high energy density lithium ion active material for battery.(4) control is convenient, can reach the effect of adjusting product cut size by pressure or the flow of regulating atomizing medium, and is simple to operate.(5) energy-conserving and environment-protective are significantly shortened the process-cycle, and the preparation time of same quantity precursor can be shortened in 1 hour by 1～2 day of coprecipitation method.Therefore with the powder by atomization technology produce anode material for lithium-ion batteries have invest little, efficient height, the excellent outstanding feature of performance.
Following constipation closes the embodiment accompanying drawing, the specific embodiment of the present invention is described in further detail, so that technical solution of the present invention is easier to understand, grasp.
Description of drawings
Fig. 1 is Fe among the embodiment 1 xMn 1-xThe Electronic Speculum figure of alloy;
Fig. 2 is LiFe among the embodiment 1 xMn 1-xPO 4Electronic Speculum figure;
Fig. 3 is LiFe among the embodiment 1 xMn 1-xPO 4The XRD diffractogram;
Fig. 4 is LiFe among the embodiment 1 xMn 1-xPO 4Discharge curve;
Fig. 5 is LiFe among the embodiment 2 0.98Mg 0.02PO 4The normal-temperature circulating performance synoptic diagram.
Embodiment
Embodiment 1
By Fe, Mn by a certain percentage (mol ratio was respectively 9: 1 or 8: 2 or 7: 3) be mixed with 100 kilograms of hybrid metals, add to heat in the intermediate frequency furnace and make its thawing, when reaching 1600 ℃～1680 ℃, temperature starts high-pressure hydraulic pump, control hydraulic pressure is 35 ± 1Mpa, and particle diameter D50 was the Fe of 1～2 μ m during high-pressure fog prepared xMn 1-xPowdered alloy, the stereoscan photograph of this powder as shown in Figure 1.The 500 ℃ of calcinings in retort furnace of this powder are obtained complex metal oxides FeMnO 3With LiH 2PO 4With the above-mentioned FeMnO that obtains 3And an amount of carbon dust (n wherein Li: n (Fe+Mn)=1.03: 1) behind the thorough mixing in nitrogen 700 ℃ of calcinings obtained height in 5 hours and shake than cathode material for lithium ion battery LiFe xMn 1-xPO 4, the stereoscan photograph of this material as shown in Figure 2, test obtains its tap density and reaches 1.8～2.0g/cm 3, specific surface area BET=9.5～12m 2/ g.The XRD diffractogram of this material as shown in Figure 3.Fig. 4 is the discharge curve and the LiFePO of this material 4And LiMnPO 4Comparison diagram.
Embodiment 2
With 100 kilograms of metal Fe, Mg (n Fe: n Mg=98: 2) gradation joins in the intermediate frequency furnace, and heating makes its thawing, starts high-pressure hydraulic pump when temperature reaches 1600 ℃～1650 ℃, and control hydraulic pressure is 35 ± 1Mpa, and particle diameter D50 was the Fe of 0.52 μ m during high-pressure fog prepared 0.98Mg 0.02Powdered alloy obtains complex metal oxides Fe with the 500 ℃ of calcinings in retort furnace of this powder 0.98Mg 0.02O 3With LiH 2PO 4With the above-mentioned Fe that obtains 0.98Mg 0.02O 3And an amount of carbon dust (n wherein Li: n (Fe+Mn)=1.03: 1) behind the thorough mixing in nitrogen 700 ℃ of calcinings obtained height in 2 hours and shake than cathode material for lithium ion battery LiFe 0.98Mg 0.02PO 4, test obtains its tap density and reaches 1.85g/cm3, specific surface area BET=9.54m 2/ g.18650 cylindrical batteries of Fig. 5 for using this material preparation to obtain, as seen from the figure, 790 capability retentions of this battery 1C charge and discharge cycles are 90.5%.
By the foregoing description as can be known, beneficial effect of the present invention is: (1) clean and effective, utilization rate of raw materials can reach more than 99.5%.And conventional coprecipitation method is because the complexing action of complexing agent (generally using ammoniacal liquor) and the influence of sedimentable matter solubleness cause utilization rate of raw materials generally in 95%, a large amount of noble metal enters filtrate with the ionic form and is difficult to recycle during production, this has not only increased cost, has also polluted human physical environment of depending on for existence.And the use of a large amount of ammoniacal liquor makes that also production environment is relatively poor in the reaction process.(2) the big panel height of throughput, at present use oxyhydroxide or carbonate etc. to be precipitation agent, ammoniacal liquor etc. are that the coprecipitation method cathode material preparation technology of complexing agent need pass through co-precipitation, a plurality of links such as ageing, complex process, 24 hours consuming time or longer, and use the powder by atomization technology with one spray of starting material fusing back, convenient and swift, can finish the production of precursor half an hour.(3) excellent performance: a, tap density height, the precursor material tap density that coprecipitation method makes is generally at 1.0g/cm 3Below, and powder particle is difficult to reach the ball-type effect; Though spray drying method for preparation also can prepare spheroidal particle, energy consumption is big, and efficient is low, and the more form with hollow ball exists.The powder by atomization technology can simply realize the powdered material ball-typeization, product tap density 1.8g/cm 3More than.B, doping conveniently only need this metal simple-substance or oxide compound etc. are melted the doping effect that just can realize that dispersion effect is high simultaneously as starting material when needing to mix other metals, so atomization are more suitable for being used as the high energy density lithium ion active material for battery.(4) control is convenient, can reach the effect of adjusting product cut size by pressure or the flow of regulating atomizing medium, and is simple to operate.(5) energy-conserving and environment-protective are significantly shortened the process-cycle, and the preparation time of same quantity precursor can be shortened in 1 hour by 1～2 day of coprecipitation method.Therefore with the powder by atomization technology produce anode material for lithium-ion batteries have invest little, efficient height, the excellent outstanding feature of performance.
The present invention still has multiple concrete embodiment, and all employings are equal to replacement or equivalent transformation and all technical schemes of forming, all drop within the scope of protection of present invention.

Claims (4)

1. cathode material for lithium ion battery LiFe xM 1-xPO 4Synthetic method, described M is selected from one or more among metallic element Mn, Fe, Ni, Co, Al, Mg, Ti and the Cu; 0≤x≤1 is characterized in that: comprise the steps:
(a) starting material configuration: according to target the content of each metallic element of product obtains raw material with raw material metal or its oxide compound by the suitable proportion collocation;
(b) presoma preparation: above-mentioned raw materials is heated to 1000 ℃～1800 ℃ by energising in the suitable order adding intermediate frequency furnace, after melting fully, it injects atomisation unit, pressure and flow by the control atomizing medium make submicron order ball-type composite metal powder, be presoma, described atomizing medium comprises water and/or gas;
(c) oxide compound preparation: sintering in the oxidizing atmosphere of the above-mentioned presoma that obtains in 200 ℃～700 ℃ temperature ranges is obtained oxide compound Fe xM yO z, 0≤x, y≤2,1≤z≤4;
(d) cathode material preparation: the oxide compound that above-mentioned reaction is obtained mixes an amount of lithium-containing compound, P contained compound and reductibility compound and obtained cathode material for lithium ion battery LiFe in once sintered at least 2～40 hours in 400 ℃～1000 ℃, inert atmosphere protection xM 1-xPO 4, 0≤x≤1.
2. cathode material for lithium ion battery LiFe according to claim 1 xM 1-xPO 4Synthetic method, it is characterized in that: lithium-containing compound is selected from Li described in the step (d) 2CO 3, LiOH, LiF, LiH 2PO 4And Li 3PO 4In one or more, the add-on of described lithium-containing compound is n in molar ratio Li: n (Fe+M)=0.9～1.1: 1.
3. cathode material for lithium ion battery LiFe according to claim 1 xM 1-xPO 4Synthetic method, it is characterized in that: P contained compound is selected from NH described in the step (d) 4H 2PO 4, (NH 4) 2HPO 4, LiH 2PO 4, Li 2HPO 4, Li 3PO 4, FePO 4And AlPO 4In one or more, the add-on of described P contained compound is n in molar ratio (Fe+M): n P=0.9～1.1: 1.
4. cathode material for lithium ion battery LiFe according to claim 1 xM 1-xPO 4Synthetic method, it is characterized in that: the reductibility compound is selected from one or more in carbon, acetylene black, sucrose and the polyvinyl alcohol described in the step (d).
CN2011100733846A 2011-03-25 2011-03-25 Method for synthesizing cathode material LiFexM1-xPO4 of lithium ion battery Pending CN102219200A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111347054A (en) * 2018-12-21 2020-06-30 财团法人金属工业研究发展中心 Magnetic powder composite material and preparation method thereof

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111347054A (en) * 2018-12-21 2020-06-30 财团法人金属工业研究发展中心 Magnetic powder composite material and preparation method thereof

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Application publication date: 20111019