CN1447466A - Method for preparing anode material of spherical lithium manganate applicable to lithium ion batteries - Google Patents
Method for preparing anode material of spherical lithium manganate applicable to lithium ion batteries Download PDFInfo
- Publication number
- CN1447466A CN1447466A CN03109127A CN03109127A CN1447466A CN 1447466 A CN1447466 A CN 1447466A CN 03109127 A CN03109127 A CN 03109127A CN 03109127 A CN03109127 A CN 03109127A CN 1447466 A CN1447466 A CN 1447466A
- Authority
- CN
- China
- Prior art keywords
- lithium ion
- positive electrode
- spherical
- lithium manganate
- mno
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000000034 method Methods 0.000 title claims abstract description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims description 11
- 229910001416 lithium ion Inorganic materials 0.000 title claims description 11
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 title claims description 10
- 239000010405 anode material Substances 0.000 title 1
- 239000000463 material Substances 0.000 claims abstract description 31
- 239000000843 powder Substances 0.000 claims abstract description 14
- 238000002360 preparation method Methods 0.000 claims description 15
- 229910015645 LiMn Inorganic materials 0.000 claims description 13
- 239000011230 binding agent Substances 0.000 claims description 7
- 238000007788 roughening Methods 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- 238000010334 sieve classification Methods 0.000 claims description 2
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 abstract 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 abstract 2
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 abstract 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract 1
- 238000000498 ball milling Methods 0.000 abstract 1
- 229910052593 corundum Inorganic materials 0.000 abstract 1
- 238000001035 drying Methods 0.000 abstract 1
- 239000004615 ingredient Substances 0.000 abstract 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 abstract 1
- 229910052808 lithium carbonate Inorganic materials 0.000 abstract 1
- 238000004321 preservation Methods 0.000 abstract 1
- 238000007873 sieving Methods 0.000 abstract 1
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000002245 particle Substances 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 238000009413 insulation Methods 0.000 description 3
- 238000012216 screening Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
Images
Classifications
-
- 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
- H01M4/04—Processes of manufacture in general
- H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
-
- 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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- 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)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The ingredient of the invented material is as following: Li2CO3: 1-1.05, MnO2: 4, Al2O3:0.01-0.02, Cr2O3: 0-0.02. LiMn2O4 is obtained by ball milling the mixed materials, drying, sieving, furnace at 700-800 deg.C and heat preservation process. The invention provides the features of even powder granularity, high imabibition quantity, capacity range 110-120 mAh/g and attenuation 5-10 % at 500 times. The average grain size of the material is 0.1 micron m and in spherical shape.
Description
Technical field
The present invention relates to spherical lithium manganate positive electrode that a kind of lithium ion battery uses and preparation method thereof, belong to the battery material preparation
Technical field.
Background technology
LiCoO
2Be the positive electrode of present commercialization lithium ion battery and since it cost an arm and a leg, be unfavorable for environmental protection, as the electrokinetic cell poor stability, just progressively by novel environmental protection positive electrode LiMn
2O
4Replace.Because LiMn
2O
4Material composition and preparation technology's is different, to LiMn
2O
4Specific capacity, loop attenuation influence is very big, has limited LiMn
2O
4Be extensive use of.At present, LiMn
2O
4The preparation method have two kinds, liquid phase method, solid reaction process.Solid reaction process, because method is simple, raw material and production cost are low, are LiMn
2O
4The main preparation methods of positive electrode.But, the LiMn of common solid reaction process preparation
2O
4, be not spheric granules, but irregular particle has influenced LiMn
2O
4Result of use.
Summary of the invention
The spherical lithium manganate positive electrode that provides a kind of lithium ion battery cheap, that be beneficial to environmental protection to use is provided in order to overcome the deficiencies in the prior art.
The spherical lithium manganate positive electrode that the lithium ion battery that the present invention proposes is used, this material is with MnO
2And Li
2CO
3Be raw material, it is characterized in that the prescription of described material is: Li
2CO
3: 1～1.05, MnO
2: 4, Al
2O
3: 0.01～0.02, Cr
2O
3: 0～0.02, its ratio is actual molal quantity.
It is simple, low-cost that another object of the present invention provides a kind of technology, the preparation method of the spherical lithium manganate positive electrode that the lithium ion battery of the powder particle form spherical in shape of preparation is used.
The preparation method of the spherical lithium manganate positive electrode that a kind of lithium ion battery is used is characterized in that, this method is carried out successively as follows:
(1) weighing is Li in molar ratio respectively
2CO
3: 1～1.05, MnO
2: 4, Al
2O
3: 0.01～0.02, Cr
2O
3: 0～0.02 prepares burden;
(2) powder of being prepared is carried out ball mill mixing;
The material oven dry that (3) will mix is sieved;
(4) material that will sieve is 700 ℃～850 ℃ calcinings, and be incubated 15 hours～25 hours;
(5) add organic binder bond in the material that will react, carry out roughening treatment;
(6) material after the above-mentioned roughening treatment pulverized, crossed sieve classification and promptly get LiMn
2O
4Powder.
In step (5), described organic binder bond is a polyvinyl alcohol.
Utilize the powder particles of prescription of the present invention and preparation method preparation even, average aggregate granularity is 20 μ m, and mean grain size is 0.1 μ m, particle shape is spherical, powder has big liquid absorption, and capacity distribution 110～120mAh/g decays to 5～10% 500 times.This preparation method technology is simple, low-cost, is applicable to suitability for industrialized production.
Description of drawings
Fig. 1 is the microstructure photograph of material of the present invention, and resolution is 2000 times.
Fig. 2 is the microstructure photograph of material of the present invention, and resolution is 100 times.
Embodiment
The present invention will be further described below in conjunction with embodiment:
Embodiment 1
(1) takes by weighing Li
2CO
318%wt, MnO
281%wt, Al
2O
31%wt, granularity is respectively 1 μ m, 20 μ m, 2 μ m;
(2) powder of being prepared is material in proportion: alcohol: ball=1: 1.5: 2 (weight), carried out ball mill mixing 12 hours;
(3) material that will mix is crossed 60 mesh sieves 50 ℃ of oven dry 12 hours;
(4) material that will sieve carries out chemical reaction 800 ℃ of insulations 20 hours;
(5) add organic binder bond in the material that will react, carry out roughening treatment;
(6) crushing screening, classification obtain the LiMn of 20 μ m
2O
4Powder.
Embodiment 2
(1) takes by weighing Li
2CO
318.1%wt, MnO
281%wt, Al
2O
30.45%wt, Cr
2O
30.45%wt, granularity is respectively 1 μ m, 20 μ m, 2 μ m, 2 μ m;
(2) in proportion with the powder prepared; Material: alcohol: ball=1: 1.5: 2 (weight), carried out ball mill mixing 12 hours;
(3) material that will mix is crossed 60 mesh sieves 50 ℃ of oven dry 12 hours;
(4) material that will sieve carries out chemical reaction 720 ℃ of insulations 25 hours;
(5) add organic binder bond in the material that will react, carry out roughening treatment;
(6) crushing screening, classification obtain the LiMn of 20 μ m
2O
4Powder.
Embodiment 3
(1) takes by weighing Li
2CO
318%wt, MnO
281%wt, Al
2O
30.40%wt, Cr
2O
30.60%wt, granularity is respectively 1 μ m, 20 μ m, 2 μ m, 2 μ m;
(2) in proportion with the powder prepared; Material: alcohol: ball=1: 1.5: 2 (weight), carried out ball mill mixing 12 hours;
(3) material that will mix is crossed 60 mesh sieves 50 ℃ of oven dry 12 hours;
(4) material that will sieve carries out chemical reaction 850 ℃ of insulations 20 hours;
(5) add organic binder bond in the material that will react, carry out roughening treatment;
(6) crushing screening, classification obtain the LiMn of 20 μ m
2O
4Powder.
Claims (3)
1, the spherical lithium manganate positive electrode used of lithium ion battery, this material is with MnO
2And Li
2CO
3Be raw material, it is characterized in that the prescription of described material is: Li
2CO
3: 1～1.05, MnO
2: 4, Al
2O
3: 0.01～0.02, Cr
2O
3: 0～0.02, its ratio is actual molal quantity.
2, a kind of preparation method of the spherical lithium manganate positive electrode used of lithium ion battery according to claim 1 is characterized in that this method is carried out successively as follows:
(1) weighing is Li in molar ratio respectively
2CO
3: 1～1.05, MnO
2: 4, Al
2O
3: 0.01～0.02, Cr
2O
3: 0～0.02 prepares burden;
(2) powder of being prepared is carried out ball mill mixing;
The material oven dry that (3) will mix is sieved;
(4) material that will sieve is 700 ℃～850 ℃ calcinings, and be incubated 15 hours～25 hours;
(5) add organic binder bond in the material that will react, carry out roughening treatment;
(6) material after the above-mentioned roughening treatment pulverized, crossed sieve classification and promptly get LiMn
2O
4Powder.
3, the preparation method of the spherical lithium manganate positive electrode of using according to the described lithium ion battery of claim 2, it is characterized in that: the described organic binder bond of step (5) is a polyvinyl alcohol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB03109127XA CN1207803C (en) | 2003-04-04 | 2003-04-04 | Method for preparing anode material of spherical lithium manganate applicable to lithium ion batteries |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB03109127XA CN1207803C (en) | 2003-04-04 | 2003-04-04 | Method for preparing anode material of spherical lithium manganate applicable to lithium ion batteries |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1447466A true CN1447466A (en) | 2003-10-08 |
| CN1207803C CN1207803C (en) | 2005-06-22 |
Family
ID=28050245
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB03109127XA Expired - Fee Related CN1207803C (en) | 2003-04-04 | 2003-04-04 | Method for preparing anode material of spherical lithium manganate applicable to lithium ion batteries |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1207803C (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100342569C (en) * | 2005-07-15 | 2007-10-10 | 广州鸿森材料有限公司 | Method for synthesizing lithium ion cell positive cell polar material rotary furnace |
| CN102201572A (en) * | 2010-03-25 | 2011-09-28 | 青岛新正锂业有限公司 | LiMn2-xMxO4.yLiAlO2 as anode material for lithium ion battery |
| CN102723474A (en) * | 2012-05-25 | 2012-10-10 | 青岛乾运高科新材料股份有限公司 | Method for preparing spheroidic lithium manganate used as lithium ion anode material |
| CN108206274A (en) * | 2016-12-17 | 2018-06-26 | 赖愉文 | It is a kind of to prepare LiHoxMn2-xO4The technique of electrode material |
| CN108206272A (en) * | 2016-12-17 | 2018-06-26 | 赖愉文 | A kind of LiMn for adulterating Gd2O4Electrode material and preparation method thereof |
| CN108206273A (en) * | 2016-12-17 | 2018-06-26 | 赖愉文 | A kind of LiMn for adulterating Tb2O4Electrode material |
| CN108203118A (en) * | 2016-12-17 | 2018-06-26 | 赖愉文 | A kind of novel LiMn2O4Electrode material and its preparation process |
| CN108305999A (en) * | 2017-12-30 | 2018-07-20 | 宁夏科捷锂电池股份有限公司 | It is a kind of to use β-Ga2O3To LiMn2O4The method that positive electrode carries out coating modification |
-
2003
- 2003-04-04 CN CNB03109127XA patent/CN1207803C/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100342569C (en) * | 2005-07-15 | 2007-10-10 | 广州鸿森材料有限公司 | Method for synthesizing lithium ion cell positive cell polar material rotary furnace |
| CN102201572A (en) * | 2010-03-25 | 2011-09-28 | 青岛新正锂业有限公司 | LiMn2-xMxO4.yLiAlO2 as anode material for lithium ion battery |
| CN102723474A (en) * | 2012-05-25 | 2012-10-10 | 青岛乾运高科新材料股份有限公司 | Method for preparing spheroidic lithium manganate used as lithium ion anode material |
| CN108206274A (en) * | 2016-12-17 | 2018-06-26 | 赖愉文 | It is a kind of to prepare LiHoxMn2-xO4The technique of electrode material |
| CN108206272A (en) * | 2016-12-17 | 2018-06-26 | 赖愉文 | A kind of LiMn for adulterating Gd2O4Electrode material and preparation method thereof |
| CN108206273A (en) * | 2016-12-17 | 2018-06-26 | 赖愉文 | A kind of LiMn for adulterating Tb2O4Electrode material |
| CN108203118A (en) * | 2016-12-17 | 2018-06-26 | 赖愉文 | A kind of novel LiMn2O4Electrode material and its preparation process |
| CN108305999A (en) * | 2017-12-30 | 2018-07-20 | 宁夏科捷锂电池股份有限公司 | It is a kind of to use β-Ga2O3To LiMn2O4The method that positive electrode carries out coating modification |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1207803C (en) | 2005-06-22 |
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