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 PDFInfo
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- 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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- licr
- positive electrode
- sol
- positive material
- secondary lithium
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical group [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 11
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 11
- 238000003980 solgel method Methods 0.000 title claims description 7
- 239000007774 positive electrode material Substances 0.000 title claims description 6
- 238000004519 manufacturing process Methods 0.000 title 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 9
- 239000000084 colloidal system Substances 0.000 claims abstract description 5
- 238000010438 heat treatment Methods 0.000 claims abstract description 5
- 238000005979 thermal decomposition reaction Methods 0.000 claims abstract description 4
- 229910001960 metal nitrate Inorganic materials 0.000 claims 1
- 239000011572 manganese Substances 0.000 abstract description 24
- 239000011651 chromium Substances 0.000 abstract description 10
- 239000000463 material Substances 0.000 abstract description 10
- 229910052804 chromium Inorganic materials 0.000 abstract description 6
- 238000002360 preparation method Methods 0.000 abstract description 6
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 abstract description 5
- 229910032387 LiCoO2 Inorganic materials 0.000 abstract description 2
- 229910002651 NO3 Inorganic materials 0.000 abstract description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 abstract description 2
- 229910052751 metal Inorganic materials 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 abstract 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 abstract 1
- 229910052748 manganese Inorganic materials 0.000 abstract 1
- 150000002739 metals Chemical class 0.000 abstract 1
- 229910015645 LiMn Inorganic materials 0.000 description 6
- 239000007787 solid Substances 0.000 description 5
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 4
- 229910012820 LiCoO Inorganic materials 0.000 description 3
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229910052573 porcelain Inorganic materials 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011282 treatment Methods 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 101100513612 Microdochium nivale MnCO gene Proteins 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 238000004320 controlled atmosphere Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 238000010671 solid-state reaction Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
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Classifications
-
- 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
-
- 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
- H01M4/485—Selection 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
-
- 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
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
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
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.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99111152A CN1102805C (en) | 1999-07-28 | 1999-07-28 | Process for preparing positive electrode material LiCrxMnx-xO4 of secondary lithium battery by sol-gel method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99111152A CN1102805C (en) | 1999-07-28 | 1999-07-28 | Process for preparing positive electrode material LiCrxMnx-xO4 of secondary lithium battery by sol-gel method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1244045A CN1244045A (en) | 2000-02-09 |
| CN1102805C true CN1102805C (en) | 2003-03-05 |
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ID=5274912
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN99111152A Expired - Fee Related CN1102805C (en) | 1999-07-28 | 1999-07-28 | Process for preparing positive electrode material LiCrxMnx-xO4 of secondary lithium battery by sol-gel method |
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| Country | Link |
|---|---|
| CN (1) | CN1102805C (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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)
| 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 |
-
1999
- 1999-07-28 CN CN99111152A patent/CN1102805C/en not_active Expired - Fee Related
Patent Citations (2)
| 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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| Publication number | Publication date |
|---|---|
| CN1244045A (en) | 2000-02-09 |
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