CN1102805C - Process for preparing positive electrode material LiCrxMnx-xO4 of secondary lithium battery by sol-gel method - Google Patents

Process for preparing positive electrode material LiCrxMnx-xO4 of secondary lithium battery by sol-gel method Download PDF

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Publication number
CN1102805C
CN1102805C CN99111152A CN99111152A CN1102805C CN 1102805 C CN1102805 C CN 1102805C CN 99111152 A CN99111152 A CN 99111152A CN 99111152 A CN99111152 A CN 99111152A CN 1102805 C CN1102805 C CN 1102805C
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Prior art keywords
licr
positive electrode
sol
positive material
secondary lithium
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CN1244045A (en
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唐致远
杨冬平
郭鹤桐
李建纲
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DALU TAIJI BATTERY Co Ltd BEIJING
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DALU TAIJI BATTERY Co Ltd BEIJING
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/052Li-accumulators
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/48Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505Selection 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
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/48Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

Abstract

The present invention relates to a novel method for preparing positive material LiCr<x>Mn<2-x>O4 (0<x<0.3) of serondary lithium batteries, a positive material used for secondary lithium batteries and a preparation method. The material is compound oxide LiCr<x>Mn<2-x>O4 (0<x<0.3) doped with chromium, lithium and manganese. The sol-gel three-step synthesis for preparing the material comprises the steps that nitrate of the used metals is dissolved in the glycol solution of citric acid according to an atomic ratio of Li to Mn to Cr: 1 to 1.05: (2-X): X to prepare colloid, and the colloid is dried at a temperature of 60 to 180 DEG C in vacuum, processed by thermal decomposition at a temperature of 200 to 300 DEG C and then processed by heat treatment at a temperature of 500 to 800DEGC for 6 to 12 hours. The positive material for secondary lithium batteries has the characteristics of high specific capacity, fine cycle performance, etc., and the average specific capacity of electric discharge of the first ten times of charge and discharge cycles is up to 128 mAh/g, so the positive material is on a par with LiCoO2, and the cost of the positive material is low.

Description

Sol-gel processing prepares positive electrode material of lithium secondary cell LiCr xMn 2-xO 4New method
One, technical field
The invention belongs to energy technology field, particularly positive electrode material of lithium secondary cell is mixed chromium complex Li-Mn-oxide LiCr xMn 2-xO 4The preparation method of (0<x<0.3), the electrode material that utilizes this method to make has characteristics such as capacity height, good cycle.
Two, background technology
Positive electrode material of lithium secondary cell LiMn 2O 4Have significant advantages such as high power capacity, low cost, low pollution, be considered to the LiCoO that continues 2Shou Xuan positive electrode afterwards, but its relatively poor cyclicity has limited its application.LiGuohua etc. (J.Electrochem.Soc., 143 (1), 178,1996) adopt doping Co, Cr, Ni to improve LiMn 2O 4Cycle performance.They are with Li 2CO 3, Mn (CHCOO) 24H 2O and Cr 2O 3Be raw material, 600 ℃ of following preliminary treatment after 6 hours, made LiCr in synthetic 3 days in 750 ℃ xMn 2-xO 4(0<x<0.33).(J.Electrochem.Soc. such as Robertson, 144 (10), 3500,1997) directly under controlled atmospher, made the low-doped positive electrode LiCr that the circulating and reversible capacity reaches 110mAh/g in 20~45 hours with the metering oxide, carbonate or the hydroxide that mix in 800 ℃ of calcinings 0.02Mn 1.98O 4Recently, D.Zhang etc. (J.PowerSources 76,81, the 1998) LiCr that adopted the high-voltage solid-state prepared in reaction xMn 2-xO 4, its specific capacity has also surpassed 110mAh/g.Though the LiCr that synthesizes in these documents xMn 2-xO 4All have than height ratio capacity and good cycle performance, but owing to all adopt solid-state reaction, raw material mixes inhomogeneous, the thermal synthesis temperature is too high, and generated time is long, easily causes the product defective, influences its specific capacity and cycle performance.
Three, summary of the invention
The objective of the invention is to overcome shortcoming of the prior art, the sol-gel process that employing can mix on atomic level is prepared the positive electrode LiCr of high power capacity, excellent cycle performance xMn 2-xO 4(0<x<0.3).
Positive electrode LiCr among the present invention xMn 2-xO 4The preparation method of (0<x<0.3) compound is: with the nitrate of used metal by Li: Mn: Cr (atomic ratio)=1~1.05: the ratio of 2-X: X is dissolved in the ethylene glycol solution of citric acid makes colloid, again through 60~180 ℃ of vacuumizes, 200~300 ℃ of thermal decompositions, 500~800 ℃ of heat treatment 6~12 hours.
Adopt bipolar electrode formula Swagelock simulated battery to LiCoO 2, LiMn 2O 4, LiCr xMn 2-xO 4(solid state process) and the chromium complex Li-Mn-oxide of mixing of the present invention carry out performance test, and the positive electrode of battery is composed as follows: 75~90% positive electrode active materials, 10~15% conductive agent acetylene blacks, 5~10% polyfluortetraethylene of binding element emulsion.The negative pole of battery is the lithium sheet, and electrolyte is 1M LiPF 61: 1 ethylene carbonate (EC)-diethyl carbonate (DEC) solution, barrier film is the Cellgard2500 micro-pore septum.
Four, description of drawings
Fig. 1 is Li/LiCoO 2The cycle performance curve of battery;
Fig. 2 is Li/LiMn 2O 4The cycle performance curve of battery;
Fig. 3 is Li/LiCr 0.1Mn 1.9O 4The cycle performance curve of (solid state process) battery;
Fig. 4 is Li/LiCr 0.05Mn 1.95O 4The cycle performance curve of (sol-gel process) battery.
Five, embodiment
The advantageous effects that shows patent of the present invention below by examples comparative.
Example 1
With Japanese imported L iCoO 2Positive electrode carries out performance test by aforementioned laminating, and typical pole piece weight is 15~20mg, diameter 1cm, in 4.25~2.75V voltage range with 0.2mA/cm 2The electric current constant current charge and discharge.Test result the figure illustrates Li/LiCoO as shown in Figure 1 2The cycle performance of battery.
Example 2
With Li 2CO 3With MnCO 3Ratio in Li: Mn (atomic ratio)=1: 2 is fully mixed, place in the porcelain crucible, in air in 600 ℃ of preliminary treatment 6 hours, then in 750 ℃ of heating 48 hours down.Products therefrom is made positive wafer thin and is carried out charge-discharge test by aforementioned, typical pole piece weight 15~20mg, and diameter 1cm is with 0.2mA/cm 2The electric current constant current charge and discharge voltage range 4.3~3.35V.Test result the figure illustrates Li/LiMn as shown in Figure 2 2O 4The cycle performance of battery.
Example 3
Press the synthetic LiCr of solid state process of Li Guohua etc. (J.Electrochem.Soc., 143 (1), 178,1996) xMn 2-xO 4, products therefrom is made positive wafer thin and is carried out charge-discharge test by aforementioned, typical pole piece weight 15~20mg, and diameter 1cm is with 0.2mA/cm 2The electric current constant current charge and discharge voltage range 4.3~3.35V.Test result the figure illustrates Li/LiCr as shown in Figure 3 0.1Mn 1.9O 4The cycle performance of (solid state process) battery.
Example 4
With lithium nitrate, manganese nitrate and chromic nitrate by Li: Mn: Cr (atomic ratio)=1: the ratio of 2-X: X is dissolved in the ethylene glycol solution of citric acid makes colloid, remove excessive solvent after precursor is made in 180 ℃ of vacuumizes in 140 ℃ of steamings, the precursor grinding is placed in the porcelain crucible, in air in 300 ℃ of thermal decompositions, then in 600 ℃ of heat treatments 8 hours.Products therefrom is made positive wafer thin and is carried out charge-discharge test by aforementioned, and condition is with example 2.Test result the figure illustrates Li/LiCr as shown in Figure 4 0.05Mn 1.95O 4The cycle performance of (sol-gel process) battery.
The test result contrast of above-mentioned each example is shown in the following table.That as can be seen from the table, adopts the present invention's [example 4] preparation mixes chromium complex Li-Mn-oxide and LiCoO 2Compare and have close specific capacity; With LiCr xMn 2-xO 4(solid state process) compared, and its specific capacity obviously improves, and cycle performance is good.Therefore, mixing the chromium complex Li-Mn-oxide and can replace LiCoO fully with the present invention preparation 2Positive electrode as lithium secondary battery.
The charge-discharge performance table of comparisons that the various materials of table 1 are preceding ten times
Example number Positive electrode Average specific capacity (mAh/g) Average size decay (mAh/ circulation)
1 LiCoO 2 120 3
2 LiMn 2O 4 97 5
3 LiCr 0.1Mn 1.9O 4 115 0.4
4 LiCr 0.05Mn 1.95O 4 128 0.5
Beneficial effect of the present invention:
Adopt its charge-discharge performance of new material of sol-gel process of the present invention preparation good, its front ten times discharge average specific capacity reaches 128mAh/g, can with LiCoO2Material compares favourably, but relatively cheap many of its cost.

Claims (1)

1. a sol-gel processing prepares positive electrode material of lithium secondary cell LiCr xMn 2-xO 4Method, it is characterized in that:
(1) metal nitrate is dissolved in the ratio of atomic ratio Li: Mn: Cr=1~1.05: 2-X: X in the ethylene glycol solution of citric acid and makes colloid, wherein 0<X<0.3;
(2) through 60~180 ℃ of vacuumizes;
(3) 200~300 ℃ of thermal decompositions;
(4) 500~800 ℃ of heat treatments made in 6~12 hours.
CN99111152A 1999-07-28 1999-07-28 Process for preparing positive electrode material LiCrxMnx-xO4 of secondary lithium battery by sol-gel method Expired - Fee Related CN1102805C (en)

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CN103715408B (en) * 2013-12-13 2016-03-16 天津大学 The sol-gel process for preparing of lithium ion battery negative material zinc titanate lithium

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5169736A (en) * 1990-08-09 1992-12-08 Varta Batterie Aktiengesellschaft Electrochemical secondary element
US5783333A (en) * 1996-11-27 1998-07-21 Polystor Corporation Lithium nickel cobalt oxides for positive electrodes

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5169736A (en) * 1990-08-09 1992-12-08 Varta Batterie Aktiengesellschaft Electrochemical secondary element
US5783333A (en) * 1996-11-27 1998-07-21 Polystor Corporation Lithium nickel cobalt oxides for positive electrodes

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