CN1738078A - Method for preparing lithium ion cell cobaltic-cobaltous oxide negative pole material - Google Patents
Method for preparing lithium ion cell cobaltic-cobaltous oxide negative pole material Download PDFInfo
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- CN1738078A CN1738078A CNA2005100150029A CN200510015002A CN1738078A CN 1738078 A CN1738078 A CN 1738078A CN A2005100150029 A CNA2005100150029 A CN A2005100150029A CN 200510015002 A CN200510015002 A CN 200510015002A CN 1738078 A CN1738078 A CN 1738078A
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- cobaltic
- manganese
- cobaltous oxide
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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
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- Y02E60/10—Energy storage using batteries
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Abstract
The invention relates to a preparing method for cobaltic-cobaltous oxide negative electrode material of lithium battery. It is characterized in the following steps: (1) arranging the cobaltous carbonate (CoCo3) into high temperature furnace to be heated for 6-24 hours in the temperature of 500-900 Deg. C, and be naturally cooled for cobaltic-cobaltous oxide (Co3O4) powder (A); (2) arranging the cobalt hydroxide (Co(OH)2) into the high temperature furnace to be heated for 12-36 hours at 200-400 Deg. C, and be cooled for cobaltic-cobaltous oxide (Co3O4) powder (B); (3) adding the manganese powder which is 2-20 % wt or the nickel manganese mixed metal powder which contains manganese as 1-100 % into the prepared cobaltic-cobaltous oxide (Co3O4) powder (A) or (B), then to be mixed uniformly for the finish product. Said invention avoids the process of ball grinding to meet the industrial producing and the produced material has the advantages as high capacity, high first charging and discharging efficiency, and stable cycle performance. The invention has significant application value and economic benefits.
Description
Technical field
The present invention relates to the preparation method of lithium ion battery negative material, particularly a kind of preparation method of lithium ion cell cobaltic-cobaltous oxide negative pole material.
Background technology
At present, superior functions such as average output voltage height, specific energy are big because lithium ion battery has, discharging voltage balance, safe and long working life, the power supply that can be used as mobile electronic products such as mobile phone, notebook computer, field camera, camera, can also be as the power supply of DVD and electric bicycle, its application is boundless.
In order further to improve the performance of lithium ion battery, people are to cobaltosic oxide (Co
3O
4) negative material carried out continuous research and development.Cobaltosic oxide (Co
3O
4) negative material has the reversible capacity higher than graphite, is subjected to this field scientific research personnel's common concern as the substitution material of silicon/carbon/graphite in lithium ion batteries negative pole.Adopt cobaltosic oxide (Co separately
3O
4) as negative material, first efficiency for charge-discharge and reversible capacity are low, cycle performance is poor.Referring to [J.Power Sources,, 109 phases: 142-147 page or leaf in 2002].Cobaltosic oxide (Co
3O
4) in add metal nickel powder after, first efficiency for charge-discharge increases, but cycle performance is indeterminate.Referring to [J.Power Sources,, 133 phases: 252-259 page or leaf in 2004].Simultaneously, prior preparation method need be carried out mechanical ball milling after adding metal nickel powder, just can make nickel-cobaltic-cobaltous oxide negative pole material, therefore can expend a large amount of energy and time, is unfavorable for large-scale industrialization production.
Summary of the invention
The objective of the invention is to overcome above-mentioned weak point, provide a kind of charge-discharge performance to stablize the preparation method of the lithium ion cell cobaltic-cobaltous oxide negative pole material of good reproducibility.
The technical solution adopted in the present invention is for achieving the above object: a kind of preparation method of lithium ion cell cobaltic-cobaltous oxide negative pole material is characterized in that implementation step is as follows:
(1) with cobalt carbonate (CoCO
3) insert in the high temperature furnace, in air atmosphere,, heating 6～24 hours in 500 ℃～900 ℃, natural cooling obtains cobaltosic oxide (Co
3O
4) powder (A);
(2) with cobalt hydroxide (Co (OH)
2) insert in the high temperature furnace, in air atmosphere,, heating 12～36 hours in 200 ℃～400 ℃, natural cooling obtains cobaltosic oxide (Co
3O
4) powder (B);
(3) with the cobaltosic oxide (Co that makes
3O
4) powder (A) or (B) in to add percentage by weight be 2%～20% manganese powder or manganese nickel mixed metal powder, wherein the content of manganese is 1%～100%, mixes to obtain product.
The invention has the beneficial effects as follows: the material that this method makes has the advantage of specific capacity height, first charge-discharge efficiency height, stable cycle performance as lithium ion battery negative.And add manganese powder or manganese nickel mixed metal powder is last does not need ball milling, as long as mix, suitable more large-scale industrialization production has significant practical value and economic benefit.Technology is simple, easy and simple to handle, and is energy-efficient, effectively reduce cost.
Description of drawings
Fig. 1 represents the charge-discharge test curve of lithium ion cell cobaltic-cobaltous oxide negative pole material when charge-discharge magnification is 0.05C that embodiment 1 is prepared;
Among the figure: 1,2,3 is three discharge curves, 1 ', 2 ', 3 ' be three charging curves.
Fig. 2 represents prepared lithium ion cell cobaltic-cobaltous oxide negative pole material of embodiment 1 and the existing cycle performance compare test curve that adds the cobaltic-cobaltous oxide negative pole material of 10% nickel metal powder.
Embodiment
Below in conjunction with accompanying drawing and preferred embodiment, to details are as follows according to embodiment provided by the invention:
With cobalt carbonate (CoCO
3) insert in the high temperature furnace, in air atmosphere,, heating 6～24 hours in 500 ℃～900 ℃, natural cooling obtains cobaltosic oxide (Co
3O
4) powder (A).With the cobaltosic oxide (Co that makes
3O
4) to add percentage by weight in the powder (A) be 2%～20% manganese metal dust, mix and promptly obtain product.As the cobaltosic oxide (Co that will make
3O
4) add 10% manganese metal dust in the powder (A) and mix.
Below can carry out routinely, be negative material with the product that makes, and acetylene black is conductive agent, and Kynoar (PVDF) is a bonding agent.The proportioning of battery cathode (weight ratio) is: active material (above-mentioned cobaltic-cobaltous oxide negative pole material): acetylene black: bonding agent=85: 5: 10.Add a certain amount of N-methyl pyrrolidone (NMP) and mix well into pasty state, be evenly coated on the Copper Foil after 10 microns, roll oven dry and obtain work electrode.With the pour lithium slice is auxiliary electrode, and electrolyte is the organic electrolyte that contains lithium ion, and barrier film is microporous polyethylene or polypropylene film, is assembled into button cell.In the voltage range of 0.01V～3.0V, on cell tester, carry out charge-discharge test with the speed of 0.05C.Test result as shown in Figure 1, three charging curves change less, invertibity is good, shows that charge-discharge performance is highly stable.This material reversible capacity first is 814mAhg
-1, first charge-discharge efficiency is 77.6%, through 20 circulations, reversible capacity is 713mAhg
-1, coulombic efficiency is more than 97%.Fig. 2 shows the comparison curves of the prepared lithium ion cell cobaltic-cobaltous oxide negative pole material of embodiment 1 and the cycle performance of the existing cobaltic-cobaltous oxide negative pole material that adds 10% nickel powder, fully shows the cycle performance that negative material that the present invention prepares has good stable.
With cobalt hydroxide (Co (OH)
2) insert in the high temperature furnace, in air atmosphere,, heating 12～36 hours in 200 ℃～400 ℃, natural cooling obtains cobaltosic oxide (Co
3O
4) powder (B), with the cobaltosic oxide (Co that makes
3O
4) to add percentage by weight in the powder (B) be 2%～20% manganese metal dust, mix and obtain product.As the cobaltosic oxide (Co that will make
3O
4) add 12% manganese metal dust in the powder (B) and mix.Below press embodiment 1 described conventional method preparation and test.The reversible capacity first that makes material is 797mAhg
-1, first charge-discharge efficiency is 79%, through 20 circulations, reversible capacity is 705mAhg
-1, coulombic efficiency is more than 96%.
Cobaltosic oxide (the Co that will make by embodiment 1
3O
4) to add percentage by weight in the powder (A) be 2%～20% manganese nickel mixed metal powder, wherein the content of manganese is 1%～100%, mixes to obtain product.Below press embodiment 1 described conventional method preparation and test.As the metal dust that adds is 10% nickel manganese mixed metal powder, and wherein the content of manganese is 50% o'clock, and the reversible capacity first of gained material is 806mAhg
-1, first charge-discharge efficiency is 78%, through 20 circulations, reversible capacity is 710mAhg
-1, coulombic efficiency is more than 96%.
Embodiment 4
Cobaltosic oxide (the Co that will make by embodiment 2
3O
4) to add percentage by weight in the powder (B) be 2%～20% manganese nickel mixed metal powder, wherein the content of manganese is 1%～100%, mixes to obtain product.Below press embodiment 1 described conventional method preparation and test.As the metal dust that adds is 15% nickel manganese mixed metal powder, and wherein the content of manganese is 60% o'clock, and the reversible capacity first of gained material is 81 5mAhg
-1, first charge-discharge efficiency is 79%, through 20 circulations, reversible capacity is 722mAhg
-1, coulombic efficiency is more than 97%.
Claims (1)
1, a kind of preparation method of lithium ion cell cobaltic-cobaltous oxide negative pole material is characterized in that implementation step is as follows:
(1) with cobalt carbonate (CoCO
3) insert in the high temperature furnace, in air atmosphere,, heating 6～24 hours in 500 ℃～900 ℃, natural cooling obtains cobaltosic oxide (Co
3O
4) powder (A);
(2) with cobalt hydroxide (Co (OH)
2) insert in the high temperature furnace, in air atmosphere,, heating 12～36 hours in 200 ℃～400 ℃, natural cooling obtains cobaltosic oxide (Co
3O
4) powder (B);
(3) with the cobaltosic oxide (Co that makes
3O
4) powder (A) or (B) in to add percentage by weight be 2%～20% manganese powder or manganese nickel mixed metal powder, wherein the content of manganese is 1%～100%, mixes to obtain product.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100150029A CN100345324C (en) | 2005-09-06 | 2005-09-06 | Method for preparing lithium ion cell cobaltic-cobaltous oxide negative pole material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100150029A CN100345324C (en) | 2005-09-06 | 2005-09-06 | Method for preparing lithium ion cell cobaltic-cobaltous oxide negative pole material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1738078A true CN1738078A (en) | 2006-02-22 |
| CN100345324C CN100345324C (en) | 2007-10-24 |
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ID=36080792
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|---|---|---|---|
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105591092A (en) * | 2014-11-18 | 2016-05-18 | 中国科学院兰州化学物理研究所 | Ni-Co-Mn composite oxide lithium ion battery anode material, preparation method and application thereof |
| CN112864378A (en) * | 2020-12-31 | 2021-05-28 | 佛山鑫宏腾科技发展有限公司 | Negative electrode material for lithium battery production and preparation method thereof |
| US11038169B2 (en) | 2016-09-13 | 2021-06-15 | Samsung Sdi Co., Ltd. | Cobalt oxide for lithium secondary battery, preparing method thereof, lithium cobalt oxide for lithium secondary battery formed from the cobalt oxide, and lithium secondary battery including positive electrode comprising the lithium cobalt oxide |
| CN113233516A (en) * | 2021-05-28 | 2021-08-10 | 金川集团股份有限公司 | Preparation method of single crystal small-granularity cobaltosic oxide |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3274016B2 (en) * | 1994-03-17 | 2002-04-15 | 日本化学工業株式会社 | Method for producing lithium cobaltate-based positive electrode active material for lithium secondary battery |
| JP2002124244A (en) * | 2000-08-07 | 2002-04-26 | National Institute Of Advanced Industrial & Technology | Separator for alkaline secondary battery and alkaline secondary battery using the same |
| CN1151971C (en) * | 2002-04-22 | 2004-06-02 | 戴振华 | Process for preparing Co3O4 |
| CN1274602C (en) * | 2003-11-18 | 2006-09-13 | 深圳市格林美高新技术有限公司 | Cobaltosic oxide preparation method for lithium ion battery |
| CN1264757C (en) * | 2003-12-05 | 2006-07-19 | 北京当升材料科技有限公司 | Cobalt oxide of lithium battery grade and its preparation method |
-
2005
- 2005-09-06 CN CNB2005100150029A patent/CN100345324C/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105591092A (en) * | 2014-11-18 | 2016-05-18 | 中国科学院兰州化学物理研究所 | Ni-Co-Mn composite oxide lithium ion battery anode material, preparation method and application thereof |
| US11038169B2 (en) | 2016-09-13 | 2021-06-15 | Samsung Sdi Co., Ltd. | Cobalt oxide for lithium secondary battery, preparing method thereof, lithium cobalt oxide for lithium secondary battery formed from the cobalt oxide, and lithium secondary battery including positive electrode comprising the lithium cobalt oxide |
| CN112864378A (en) * | 2020-12-31 | 2021-05-28 | 佛山鑫宏腾科技发展有限公司 | Negative electrode material for lithium battery production and preparation method thereof |
| CN113233516A (en) * | 2021-05-28 | 2021-08-10 | 金川集团股份有限公司 | Preparation method of single crystal small-granularity cobaltosic oxide |
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| Publication number | Publication date |
|---|---|
| CN100345324C (en) | 2007-10-24 |
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Granted publication date: 20071024 Termination date: 20210906 |