CN103280576B - The positive electrode of lithium rechargeable battery and manufacture method thereof - Google Patents
The positive electrode of lithium rechargeable battery and manufacture method thereof Download PDFInfo
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- CN103280576B CN103280576B CN201310222983.9A CN201310222983A CN103280576B CN 103280576 B CN103280576 B CN 103280576B CN 201310222983 A CN201310222983 A CN 201310222983A CN 103280576 B CN103280576 B CN 103280576B
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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
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- 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 discloses positive electrode and the manufacture method thereof of lithium rechargeable battery, the positive electrode of described lithium rechargeable battery is with general formula Li
xni
1-y-zco
ymn
zmg
ati
bal
co
2represent, 0.95≤x≤1.30,0≤y≤0.6,0≤z≤0.8, wherein, y+z & lt; 1,0≤a≤0.1,0≤b≤0.1,0≤c≤0.1.The present invention can provide the positive active material for lithium secondary battery employing the lithium nickel cobalt manganese system complex oxide can giving lithium secondary battery cycle characteristics excellent especially, the lithium secondary battery this positive active material being carried out the method that manufactures and the particularly cycle characteristics excellence that employs this positive active material by industrial favourable method.
Description
Technical field
The present invention is specifically related to positive electrode and the manufacture method thereof of lithium rechargeable battery.
Background technology
In recent years, universal and miniaturized along with the portable machine such as mobile phone, notebook computer, the nonaqueous electrolytic solution secondary batteries such as lithium rechargeable battery are progressively used as its power supply.And, from the environmental problem that reply is nearest, it can be used as the traction-type cell of electric automobile etc. also to cause concern gradually.
As positive active material for lithium secondary battery, usually, extensively LiCoO is adopted
2(cobalt acid lithium) is as the material that can form 4V level secondary cell.Use LiCoO
2during as positive active material, discharge capacity is about 160mA/g, is practical as LiCo0
2the cobalt of raw material be scarce resource, and skewness, therefore Expenses Cost, raw material supplying is unstable.
Summary of the invention
Goal of the invention: the object of the invention is to make up the deficiencies in the prior art, provides a kind of lithium-contained composite oxide and manufacture method thereof of lithium electronics anode of secondary battery.
The technical solution used in the present invention: the positive electrode of lithium rechargeable battery, the positive electrode of described lithium rechargeable battery is with general formula Li
xni
1-y-zco
ymn
zmg
ati
bal
co
2represent, 0.95≤x≤1.30,0≤y≤0.6,0≤z≤0.8, wherein, y+z<1,0≤a≤0.1,0≤b≤0.1,0≤c≤0.1.
As optimization: the weight content of the weight content of described Mg atom to be the weight content of 0.001-5%, Ti atom be 0.001-5%, Al atom is 0.001-5%.
As preferably: 1.00≤x≤1.05, reason is that the initial discharge capacity of lithium secondary battery has the tendency uprised; From viewpoint 0.1≤y≤0.3 of the fail safe of lithium secondary battery; 0.1≤z≤0.3, reason is that the initial discharge capacity of lithium secondary battery has the tendency uprised.
The weight content of Mg atom is 0.05-2%, the weight content of Ti atom is 0.05-2%, its reason is, if Mg, the content of Ti atom is with Mg, Ti atom meter is lower than 0.01 % by weight, then in the lithium secondary battery employing this positive active material, there is the tendency that can not get sufficient cycle characteristics, on the other hand, if Mg, the content of Ti atom is with Mg, Ti atom meter more than 10 % by weight, then, in the lithium secondary battery employing this positive active material, has the tendency that can not get sufficient initial discharge capacity.
The weight content of Al atom is 0.2-2%, its reason is, if the content of Al atom in Al atom lower than 0.01 % by weight, then in the lithium secondary battery employing this positive active material, have the tendency that can not get sufficient cycle characteristics, on the other hand, if the content of Al atom in Al atom more than 5 % by weight, then in the lithium secondary battery employing this positive active material, there is the tendency that can not get sufficient initial discharge capacity.
As optimization: the manufacture method of the positive electrode of described lithium rechargeable battery, by lithium compound, comprise nickle atom, the compound of cobalt atom and manganese atom, titanium oxide, magnesium carbonate and aluminium oxide, these three kinds of materials with lithium atom relative to nickle atom, cobalt atom, manganese atom, titanium atom, the atomic ratio (Li/{Ni+Co+Mn+Ti+Mg+Al}) of magnesium atom and aluminium atom be more than 0.98 mode quantitatively mix, then the positive electrode needed for calcining generation, calcining heat controls between 900-1000 DEG C, calcining calcines 1-30 hour in an atmosphere or in oxygen atmosphere, carry out suitably cooling after calcining and pulverize as required.
As optimization: described in comprise nickle atom, manganese atom and cobalt atom compound be cohesion shape complex hydroxide.
As optimization: described in comprise the compound of nickle atom, cobalt atom and manganese atom, be 0.2-1.0mol relative to 1mol nickle atom cobalt atom, manganese atom is 0.2-3.0mol ratio presents.
As optimization: the weight content of LiOH remaining in the positive electrode of described lithium rechargeable battery below 0.15%, remaining Li
2cO
3weight content below 0.4%.
As preferably: from the view point of becoming the excellent battery of particularly cycle characteristics, lithium compound, comprise the compound of nickle atom, cobalt atom and manganese atom, titanium oxide, magnesium carbonate and aluminium oxide, these three kinds of materials quantitatively mix for the mode between 1.01-1.10 with the atomic ratio (Li/{Ni+Co+Mn+Ti+Mg+Al}) of lithium atom relative to nickle atom, cobalt atom, manganese atom, titanium atom, magnesium atom and aluminium atom; Calcining heat controls between 900-950 DEG C; From the view point of suppress coating gelation, suppress cell expansion, the weight content of LiOH remaining in the positive electrode of lithium rechargeable battery below 0.05%, remaining Li
2cO
3weight content below 0.3%.
Beneficial effect: the present invention can provide the positive active material for lithium secondary battery employing the lithium nickel cobalt manganese system complex oxide can giving lithium secondary battery cycle characteristics excellent especially, the lithium secondary battery this positive active material being carried out the method that manufactures and the particularly cycle characteristics excellence that employs this positive active material by industrial favourable method.
Embodiment
Below in conjunction with specific embodiment, the invention will be further described:
Embodiment 1:
The positive electrode of lithium rechargeable battery, the positive electrode of lithium rechargeable battery is with general formula Li
xni
1-y-zco
ymn
zmg
ati
bal
co
2represent, x is 1.00, y be 0.1, z be 0.1, a be 0, b be 0, c is 0.The weight content of the weight content of Mg atom to be the weight content of 0.05%, Ti atom be 0.05%, Al atom is 0.2%.
The manufacture method of the positive electrode of lithium rechargeable battery, by lithium compound, comprise nickle atom, the compound of cobalt atom and manganese atom, titanium oxide, magnesium carbonate and aluminium oxide, these three kinds of materials with lithium atom relative to nickle atom, cobalt atom, manganese atom, titanium atom, the atomic ratio (Li/{Ni+Co+Mn+Ti+Mg+Al}) of magnesium atom and aluminium atom be 1.01 mode quantitatively mix, then the positive electrode needed for calcining generation, calcining heat controls at 900 DEG C, calcining is calcined 1 hour in an atmosphere or in oxygen atmosphere, carry out suitably cooling after calcining and pulverize as required.Comprise the compound of nickle atom, manganese atom and cobalt atom for cohesion shape complex hydroxide.Comprise the compound of nickle atom, cobalt atom and manganese atom, be 0.2mol relative to 1mol nickle atom cobalt atom, manganese atom is 0.2mol ratio presents.The weight content of LiOH remaining in the positive electrode of lithium rechargeable battery below 0.05%, remaining Li
2cO
3weight content below 0.3%.
Embodiment 2:
The positive electrode of lithium rechargeable battery, the positive electrode of lithium rechargeable battery is with general formula Li
xni
1-y-zco
ymn
zmg
ati
bal
co
2represent, x is 1.05, y be 0.3, z be 0.3, a be 0.1, b be 0.1, c is 0.1.The weight content of the weight content of Mg atom to be the weight content of 2%, Ti atom be 2%, Al atom is 2%.
The manufacture method of the positive electrode of lithium rechargeable battery, by lithium compound, comprise nickle atom, the compound of cobalt atom and manganese atom, titanium oxide, magnesium carbonate and aluminium oxide, these three kinds of materials with lithium atom relative to nickle atom, cobalt atom, manganese atom, titanium atom, the atomic ratio (Li/{Ni+Co+Mn+Ti+Mg+Al}) of magnesium atom and aluminium atom be 1.10 mode quantitatively mix, then the positive electrode needed for calcining generation, calcining heat controls at 950 DEG C, calcining is calcined 30 hours in an atmosphere or in oxygen atmosphere, carry out suitably cooling after calcining and pulverize as required.Comprise the compound of nickle atom, manganese atom and cobalt atom for cohesion shape complex hydroxide.Comprise the compound of nickle atom, cobalt atom and manganese atom, be 1.0mol relative to 1mol nickle atom cobalt atom, manganese atom is 3.0mol ratio presents.The weight content of LiOH remaining in the positive electrode of lithium rechargeable battery below 0.05%, remaining Li
2cO
3weight content below 0.3%.
Embodiment 3:
The positive electrode of lithium rechargeable battery, the positive electrode of lithium rechargeable battery is with general formula Li
xni
1-y-zco
ymn
zmg
ati
bal
co
2represent, x is 1.02, y be 0.2, z be 0.2, a be 0.05, b be 0.03, c is 0.04.The weight content of the weight content of Mg atom to be the weight content of 1.05%, Ti atom be 1.10%, Al atom is 1.2%.
The manufacture method of the positive electrode of lithium rechargeable battery, by lithium compound, comprise nickle atom, the compound of cobalt atom and manganese atom, titanium oxide, magnesium carbonate and aluminium oxide, these three kinds of materials with lithium atom relative to nickle atom, cobalt atom, manganese atom, titanium atom, the atomic ratio (Li/{Ni+Co+Mn+Ti+Mg+Al}) of magnesium atom and aluminium atom be 1.05 mode quantitatively mix, then the positive electrode needed for calcining generation, calcining heat controls at 930 DEG C, calcining is calcined 15 hours in an atmosphere or in oxygen atmosphere, carry out suitably cooling after calcining and pulverize as required.Comprise the compound of nickle atom, manganese atom and cobalt atom for cohesion shape complex hydroxide.Comprise the compound of nickle atom, cobalt atom and manganese atom, be 0.8mol relative to 1mol nickle atom cobalt atom, manganese atom is 1.8mol ratio presents.The weight content of LiOH remaining in the positive electrode of lithium rechargeable battery below 0.05%, remaining Li
2cO
3weight content below 0.3%.
Claims (1)
1. the positive electrode of lithium rechargeable battery, is characterized in that: the positive electrode of described lithium rechargeable battery is with general formula Li
xni
1-y-zco
ymn
zmg
ati
bal
co
2represent, 1.00≤x≤1.05, 0.1≤y≤0.3, 0.1≤z≤0.3, wherein, y+z<1, 0≤a≤0.1, 0≤b≤0.1, 0≤c≤0.1, the manufacture method of the positive electrode of described lithium rechargeable battery: by lithium compound, comprise nickle atom, the compound of cobalt atom and manganese atom, titanium oxide, magnesium carbonate and aluminium oxide, with atomic ratio Li/ (Ni+Co+Mn+Ti+Mg+Al) for the mode between 1.01-1.10 quantitatively mixes, then the positive electrode needed for calcining generation, calcining heat controls between 900-950 DEG C, calcining calcines 1-30 hour in an atmosphere or in oxygen atmosphere, carry out suitably cooling after calcining and pulverize as required, the weight content of LiOH remaining in the positive electrode of described lithium rechargeable battery is below 0.05%, remaining Li
2cO
3weight content below 0.3%, the weight content of Mg atom is 0.05-2%, the weight content of Ti atom is 0.05-2%, the weight content of Al atom is 0.2-2%, the described compound comprising nickle atom, cobalt atom and manganese atom is cohesion shape complex hydroxide, and be 0.2-1.0mol relative to 1mol nickle atom cobalt atom, manganese atom is 0.2-3.0mol ratio presents.
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103500827B (en) * | 2013-10-11 | 2017-05-24 | 宁德新能源科技有限公司 | Lithium ion battery and multi-element positive material thereof as well as preparation method of multi-element positive material |
| JP6654793B2 (en) * | 2014-07-17 | 2020-02-26 | マクセルホールディングス株式会社 | Positive electrode for non-aqueous electrolyte secondary battery, non-aqueous electrolyte secondary battery and system thereof |
| KR102665408B1 (en) * | 2016-04-15 | 2024-05-09 | 삼성에스디아이 주식회사 | Positive active material for rechargeable lithium battery and rechargeable lithium battery including same |
| CN106532029A (en) * | 2016-12-28 | 2017-03-22 | 四川富骅新能源科技有限公司 | High-voltage ternary positive electrode material for lithium-ion battery and preparation method of high-voltage ternary positive electrode material |
| US11764355B2 (en) * | 2020-01-22 | 2023-09-19 | Uchicago Argonne, Llc | Cathode active materials for secondary batteries |
| GB202004511D0 (en) * | 2020-03-27 | 2020-05-13 | Johnson Matthey Plc | Cathode material and process |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102509784A (en) * | 2011-10-17 | 2012-06-20 | 北大先行科技产业有限公司 | Preparation method of lithium ion battery ternary cathode material |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102509784A (en) * | 2011-10-17 | 2012-06-20 | 北大先行科技产业有限公司 | Preparation method of lithium ion battery ternary cathode material |
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