CN1221225A - Method for preparing lithium ion battery active material superfines with spray drying method - Google Patents

Method for preparing lithium ion battery active material superfines with spray drying method Download PDF

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Publication number
CN1221225A
CN1221225A CN98120366A CN98120366A CN1221225A CN 1221225 A CN1221225 A CN 1221225A CN 98120366 A CN98120366 A CN 98120366A CN 98120366 A CN98120366 A CN 98120366A CN 1221225 A CN1221225 A CN 1221225A
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ion battery
lithium ion
active material
spray drying
battery active
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CN98120366A
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CN1089193C (en
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万春荣
李阳兴
姜长印
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Tsinghua University
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Tsinghua University
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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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • 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

A spray drying process for preparing the ultrafine powder of active material for lithium ion battery includes such steps as weighing raw materials by chemical metering ratio,mixing, adding deionized water and thickening agent, spray dring the solution to obtain powder, and sintering at a certain temp. The product has excellent chemical properties.

Description

The method of spray drying method for preparation lithium ion battery active material superfine powder
The present invention relates to a kind of method of spray drying method for preparation lithium ion battery active material superfine powder, belong to materials science field.
In advanced information society, be accompanied by the develop rapidly of mobile communication and mobile computing, GSM (GlobalSystem for Mobile Communication), DECT (Digital European Cordless), PHC products such as (Personal Handy Computer) are unprecedentedly active, make people become increasingly conspicuous for the requirement of high-performance chemical power supply.Lithium ion battery since have output voltage height, energy density big, have extended cycle life, the advantage of memory-less effect etc., therefore since the nineties, become the focus of research and development always.
Lithium one compound transition metal oxide is as LiCoO 2, LiNiO 2, LiMn 2O 4And LiV 3O 8Deng, all be the anode active material of lithium ion battery of excellent performance.Based on the compound transition metal oxide of Sn, because Li +The insertion electromotive force lower, be the lithium ion battery negative material of the excellent performance that emerges in recent years.This based composite oxide has all possessed the feature of topochemical reaction: in the process of charging, and Li +From composite oxides, deviate to embed in the negative material; At discharge process then in contrast.As Li wherein +Concentration when certain limit changes, because the polyvalency of transition metal can not influence the variation of compound structure and pattern.
At present, the method for preparing lithium ion battery active material is a lot, as solid reaction process, coprecipitation, sol-gal process etc.Generally, traditional synthetic method all adopts solid reaction process, is characterized in that reactant obtains active material by repetitious grinding, pulverizing, sintering, and what have also needs by auxiliary processes such as granulation or compressing tablets.The process of sintering also is long, generally needs 12～96 hours, even the longer time.
The objective of the invention is to propose a kind of method of spray drying method for preparation lithium ion battery active material superfine powder, by spray drying process (Spray Drying, be called for short the SD method), in the short period of time, under the lower sintering temperature and obtain the evenly ultra-fine lithium ion battery active material of no dephasign under the better simply process conditions.
Prepared lithium ion battery active material is positive electrode and negative material in the method for the spray drying method for preparation lithium ion battery active material superfine powder that the present invention proposes, and the molecular formula of positive electrode is: LiCoO 2, LiNiO 2And LiMnO 4In any, the molecular formula of negative material is: SnMnO 2Or SnB 0.5P 0.5O 3, its preparation method comprises following each step:
(1) raw material is prepared: with the raw material of the required preparing product of stoichiometric proportion weighing, and with its mixing;
(2) solution allocation: above-mentioned mixture adds deionized water, be made into the solution of 0.05～1.0mol/l, and add a certain amount of macromolecular compound as thickener, and mass percent is 5～30%, thickener is any in polyethylene glycol, polyacrylic acid or the polyvinyl alcohol;
(3) spray drying: with the spray-dried mixed powder that obtains of the solution that is made into, with pneumatic spray drying device drying, adopt and the fluidized drying mode, atomising device adopts two streaming nozzles, feedstock solution peristaltic pump sample introduction, and speed is 12～20ml/min; The orifice gas flow is controlled by compressed-air actuated pressure, produces atomizing under about 0.1MPa; The control temperature of inlet air is 300～400 ℃, and outlet is 100～200 ℃; Outlet air separates emptying through the one-level vortex;
(4) sintering of mixed powder: mixed powder can obtain to have the lithium ion battery active material superfine powder of good electric chemical property in 4～20 hours at 500～1200 ℃ of sintering.
Present technique not only is applicable to the preparation anode material for lithium-ion batteries, as Li xCoO 2, Li xNiO 2, Li xMn 2O 4, Li xMnO 2, Li xV 3O 8, and multicomponent system, as Li xCo aNi 1-aO 2, Li xCo bV 1-bO 2, Li xCo cB 1-cO 2, Li xNi aCo 1-aO 2, Li xNi bMn 1-bO 2, Li xMn bV 2-bO 4, Li xMn bCu 2-bO 4, Li xMn bAl 2-bO 4, Li xV cCo 3-cO 8(0.5≤x≤1.5,0.5≤a≤1.0,0.5≤b≤0.98,0.85≤c≤0.99) etc.; Also being suitable for preparing oxide is main lithium ion battery negative material, as SnMnO z, SnTiO z, SnCoO z, SnVO z, SnNiO z, SnCuO z, SnWO zDeng, and multicomponent system, as SnB eP fO z, SnAl dB eO z, SnAl dB eM fO z, SnAl dSi eO z, SnAl dSi eM fO z(M=P, Mg, F, K, Ba etc., 0.1≤d≤1.0,0≤e≤0.65,0≤f≤0.5,2≤z≤5) etc.
For anode material for lithium-ion batteries, raw material is mainly A+B+C three classes: category-A is water-soluble lithium salts (as lithium nitrate, a lithium acetate etc.); Category-B is water-soluble cobalt salt, nickel salt, manganese salt, vanadic salts etc.: the C class is a thickener, it is water-soluble macromolecular compound (as polyethylene glycol (PEG), polyacrylic acid (PAA), polyvinyl alcohol (PVA), a methylcellulose etc.), or organic acid (as adipic acid, maleic acid etc.) that can polymerization reaction take place in water.
For lithium ion battery negative material, raw material is mainly A+B+C three classes: category-A is the water soluble tin compound: category-B is water-soluble cobalt salt, nickel salt, manganese salt, vanadic salts etc.; The C class is water-soluble macromolecular compound (as polyethylene glycol (PEG), polyacrylic acid (PAA), polyvinyl alcohol (PVA), a methylcellulose etc.).
The lithium ion battery active material superfine powder of utilizing the present invention to prepare has the excellent in chemical performance, and the preparation method can be directly used in the large-scale industrial production of lithium ion battery active material.
Description of drawings:
Fig. 1 is the differential thermal thermogravimetric analysis curve that utilizes the superfine powder of method preparation of the present invention.
Fig. 2 is the x-ray diffraction spectra of lithium cobalt oxide.
Fig. 3 is LiCoO 2The superfine powder stereoscan photograph.
Fig. 4 is LiCoO 2Powder initial charge curve.
Fig. 5 is LiCoO 2Powder is discharge curve first.
Introduce embodiments of the invention below.
Embodiment 1:
With Li: Co mol ratio 1: 1 proportioning weighing lithium acetate and cobalt acetate, and take by weighing 5% macromolecular compound polyethylene glycol (PEG), add the solution that deionized water is made into 0.1mol/l.Resulting solution pneumatic spray drying device drying, feedstock solution peristaltic pump sample introduction, speed is 12ml/min; The orifice gas flow is controlled by compressed-air actuated pressure, produces atomizing under about 0.1MPa; The control temperature of inlet air is 300 ℃, and outlet is 100 ℃; Outlet air separates emptying through the one-level vortex.The mixed powder of the polyethylene glycol of spray drying gained and lithium acetate, cobalt acetate promptly obtains LiCoO at 800 ℃ of sintering through 4 hours 2Superfine powder.
Analyze by the data to the differential thermal thermogravimetric analysis curve of Fig. 1, the mixed powder that obtains of spray drying showed as the gain and loss situation of moisture content substantially in that just fundamental reaction is complete below 300 ℃ before 180 ℃ as can be seen, and the supporter inhales heat release simultaneously; Between 180 ℃～300 ℃, the TGA curve table reveals three significantly weightlessness: respectively at 187 ℃, 231 ℃, 241 ℃, three tangible exothermic peaks are arranged simultaneously in the DTA curve; After 300 ℃, almost zero gravity loss shows at this to be the formation of crystalline phase and perfect more than temperature.
Fig. 2 is the x-ray diffraction spectra of prepared lithium cobalt oxide, and as seen from the figure, 800 ℃ of sintering are after 4 hours, gets final product to such an extent that have α-NaFeO 2The HT-LiCoO of layer structure 2, showing as 2 θ values is the three strongest ones peak corresponding to (003), (101), (104) of 18.90 °, 37.40 °, 45.24 ° appearance, and does not occur other dephasign peaks substantially.
Fig. 3 is the LiCoO that makes 2The photo of superfines ESEM can obtain LiCoO from figure 2Some information of powder.(a) be LiCoO 2The SEM figure of 3K, what as seen make is the fine powder that particle diameter is obviously reunited than homogeneous, smooth surface, nothing; (b) be LiCoO 2The SEM of 20K figure, by visible its particle of ESEM scale big 700nm arranged approximately, little is about 200nm.
The test of chemical property is mainly tested its charge/discharge capacity by being assembled into test cell.Anode is by 80% LiCoO 2Powder and 20% TAB (polytetrafluoroethylene+acetylene black) constitute, and electrolyte is 1MLiPF 6+ EC: DMC (1: 1) is a metal lithium sheet with reference to negative pole.Charging and discharging currents density is 0.5mA/cm 2, voltage is 3.0～4.3V.Fig. 4 is LiCoO 2The initial charge curve of powder, as seen from the figure, there is a tangible charging platform in it about 4.0v in charging process, and its charging capacity is 148mAh/g; Fig. 5 is LiCoO 2Corresponding to charging curve, there is a tangible discharge platform in the discharge curve first of powder about 3.9v, discharge capacity is 135mAh/g, and efficiency for charge-discharge is 91.22%.
Other embodiment sees Table 1, and AC is the abbreviation of acetate in the table.
Table 1
Numbering Prepared active goods and materials Raw material Spray inlet temperature (℃) The spray outlet temperature (℃) Sintering temperature (℃) Sintering time (hour) Can utilize capacity (mAh/g)
??2 ???LiCoO 2 ?LiNO 3+Co(NO 3) 2+PEG(5％) ???300 ???100 ????700 ????4 ????135
?LiAC+Co(NO 3) 2+PEG(5％) ???300 ???130 ????800 ????4 ????144
?LiNO 3+Co(AC) 2+PEG(5％) ???300 ???120 ????800 ????4 ????146
??3 ???LiNiO 2 ?LiNO 3+Ni(NO 3) 2+PAA(5％) ???300 ???130 750 (logical oxygen) ????8 ????160
??4 ???LiMn 2O 4 ?LiAC+Mn(NO 3) 2+PAA(5％) ???300 ???130 ????800 ????4 ????130
?LiNO 3+Mn(NO 3) 2+PAA(5％) ???300 ???130 ????750 ????4 ????128
?LiNO 3+Mn(AC) 2+PVA(5％) ???300 ???130 ????800 ????4 ????133
?LiAC+Mn(AC) 2+PEG(5％) ???300 ???130 ????750 ????4 ????128
??5 ???SnMnO 2 ?Sn(AC) 2+Mn(AC) 2+PVA(5％) ???300 ???130 ????1000 ????6 ????498
??6 SnB 0.5P 0.5O 3 ?Sn(AC) 2+HBO 3+H 3PO 4+PVA ?(5％) ???300 ???130 ????1000 ????6 ????520

Claims (1)

1, a kind of method of spray drying method for preparation lithium ion battery active material superfine powder is characterized in that, prepared lithium ion battery active material is positive electrode and negative material, and the molecular formula of positive electrode is: LiCoO 2, LiNiO 2And LiMnO 4In any, the molecular formula of negative material is: SnMnO 2Or SnB 0.5P 0.5O 3, its preparation method comprises following each step:
(1) raw material is prepared: with the raw material of the required preparing product of stoichiometric proportion weighing, and with its mixing;
(2) solution allocation: above-mentioned mixture adds deionized water, be made into the solution of 0.05～1.0mol/l, and add a certain amount of macromolecular compound as thickener, and mass percent is 5～30%, thickener is any in polyethylene glycol, polyacrylic acid or the polyvinyl alcohol;
(3) spray drying: with the spray-dried mixed powder that obtains of the solution that is made into;
(4) sintering of mixed powder: mixed powder was the lithium ion battery active material superfine powder in 4～20 hours at 500～1200 ℃ of sintering.
CN98120366A 1998-10-09 1998-10-09 Method for preparing lithium ion battery active material superfines with spray drying method Expired - Fee Related CN1089193C (en)

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1310369C (en) * 2000-04-04 2007-04-11 索尼株式会社 Non-aqueous electrolyte secondary battery
WO2010099864A1 (en) * 2009-03-03 2010-09-10 Umicore Process for preparing alloy composite negative electrode material for lithium ion batteries
CN102484241A (en) * 2009-03-03 2012-05-30 尤米科尔公司 Process for preparing alloy composite negative electrode material for lithium ion batteries
CN103985855A (en) * 2013-12-16 2014-08-13 青岛乾运高科新材料股份有限公司 Preparation method of lithium battery cathode material solid solution micropowder
CN104064754A (en) * 2014-06-27 2014-09-24 胡莹 Preparation method of lithium and manganese oxide
CN104332623A (en) * 2014-09-09 2015-02-04 上海纳米技术及应用国家工程研究中心有限公司 Preparation method of lithium ion secondary battery negative material manganese cobalt oxide
CN106564940A (en) * 2016-10-28 2017-04-19 昆明理工大学 Nano-scale tin dioxide micro-particle preparation method
CN109809497A (en) * 2019-01-17 2019-05-28 合肥国轩高科动力能源有限公司 A kind of ullrasonic spraying calcining synthesis LiCoO2The method and its application of powder
CN110311128A (en) * 2019-07-10 2019-10-08 深圳市本征方程石墨烯技术股份有限公司 A kind of lithium cobaltate cathode material and preparation method thereof of graphene doping

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1310369C (en) * 2000-04-04 2007-04-11 索尼株式会社 Non-aqueous electrolyte secondary battery
CN100394639C (en) * 2000-04-04 2008-06-11 索尼株式会社 Non-aqueous electrolyte secondary battery
WO2010099864A1 (en) * 2009-03-03 2010-09-10 Umicore Process for preparing alloy composite negative electrode material for lithium ion batteries
CN102484241A (en) * 2009-03-03 2012-05-30 尤米科尔公司 Process for preparing alloy composite negative electrode material for lithium ion batteries
CN103985855A (en) * 2013-12-16 2014-08-13 青岛乾运高科新材料股份有限公司 Preparation method of lithium battery cathode material solid solution micropowder
CN104064754A (en) * 2014-06-27 2014-09-24 胡莹 Preparation method of lithium and manganese oxide
CN104332623A (en) * 2014-09-09 2015-02-04 上海纳米技术及应用国家工程研究中心有限公司 Preparation method of lithium ion secondary battery negative material manganese cobalt oxide
CN106564940A (en) * 2016-10-28 2017-04-19 昆明理工大学 Nano-scale tin dioxide micro-particle preparation method
CN109809497A (en) * 2019-01-17 2019-05-28 合肥国轩高科动力能源有限公司 A kind of ullrasonic spraying calcining synthesis LiCoO2The method and its application of powder
CN109809497B (en) * 2019-01-17 2021-10-01 合肥国轩高科动力能源有限公司 Ultrasonic spray calcination synthesis of LiCoO2Method for preparing powder and application thereof
CN110311128A (en) * 2019-07-10 2019-10-08 深圳市本征方程石墨烯技术股份有限公司 A kind of lithium cobaltate cathode material and preparation method thereof of graphene doping

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