CN102064314A - Anode piece of lithium ion secondary battery - Google Patents
Anode piece of lithium ion secondary battery Download PDFInfo
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- CN102064314A CN102064314A CN2010105951927A CN201010595192A CN102064314A CN 102064314 A CN102064314 A CN 102064314A CN 2010105951927 A CN2010105951927 A CN 2010105951927A CN 201010595192 A CN201010595192 A CN 201010595192A CN 102064314 A CN102064314 A CN 102064314A
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- pole piece
- anode
- lithium ion
- ion secondary
- lithium
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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
- 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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Abstract
The invention discloses an anode piece of a lithium ion secondary battery, which comprises an anode collector and an anode membrane attached on the anode collector, wherein the anode membrane internally contains uniformly distributed lithium orthophosphate. The lithium orthophosphate is uniformly distributed in the anode membrane of the anode piece of the lithium ion secondary battery and has stronger resistance to oxidation and can weaken the oxidization of anode active matters to an electrolyte under high potential. The lithium orthophosphate has stronger performance of conducting lithium ions, thus the interface resistance of the anode active matters and the electrolyte can be effectively reduced, the polarization potential and the oxidization of the anode active matters are reduced, and the circulating performance of the lithium ion battery under high potential is improved.
Description
Technical field
The present invention relates to a kind of lithium ion secondary battery positive electrode pole piece, especially a kind of anode pole piece that can improve the cycle performance of lithium rechargeable battery.
Background technology
Lithium rechargeable battery has high-energy-density, high voltage, low self-discharge rate and advantage such as in light weight, therefore is widely used in the various portable mobile electronic devices such as notebook computer, digital camera, mobile phone, MP3, MP4.
Along with portable mobile electronic device develops to miniaturization, multifunction direction, people are more and more higher to the requirement of the energy density of lithium rechargeable battery.In order to improve the energy density of lithium rechargeable battery, prior art has adopted the multiple technologies scheme, and for example, the charging that improves lithium rechargeable battery is by voltage.But, improve the oxidizability of charging when voltage can increase positive pole at high potential, promote the reaction between positive pole and the electrolyte, cause that cycle performance of battery worsens.In addition, though positive active material is carried out structure doping or the surperficial cycle performance that also can improve lithium rechargeable battery that coats, structure doping or surface coating processing procedure are numerous and diverse, have increased battery cost.
In view of this, necessaryly provide a kind of anode pole piece that improves the cycle performance under the lithium rechargeable battery high potential.
Summary of the invention
The objective of the invention is to: a kind of anode pole piece that improves the cycle performance under the lithium rechargeable battery high potential is provided.
To achieve these goals, the invention provides a kind of lithium ion secondary battery positive electrode pole piece, it comprises plus plate current-collecting body and attached to the anodal diaphragm on the plus plate current-collecting body, wherein, contains equally distributed lithium phosphate in the anodal diaphragm.
With respect to prior art, lithium ion secondary battery positive electrode pole piece of the present invention has the following advantages at least: at first, lithium phosphate has stronger non-oxidizability, can weaken the oxidation of positive electrode active material confrontation electrolyte under the high potential; Secondly, the performance of lithium phosphate conductive lithium ion is very strong, can effectively reduce the interface resistance of positive active material and electrolyte, reduces the polarization potential and the oxidizability of positive active material, improves the cycle performance under the lithium rechargeable battery high potential.
As a kind of improvement of lithium ion secondary battery positive electrode pole piece of the present invention, in the described anodal diaphragm, the weight content of lithium phosphate is 0.1% to 5.0%.When the weight content of the lithium phosphate in the anodal diaphragm less than 0.1% the time, the high voltage cycle performance of battery is not obviously improved; When the weight percentage of the lithium phosphate in the anodal diaphragm greater than 5% the time positive active material--transition metal oxide and derivative thereof are (as LiCoO because the density of lithium phosphate is far below commonly used
2And doping or surface coated derivative, LiNiCoMnO
2And doping or surface coated derivative, LiNi
0.5Mn
1.5O
2And doping or surface coated derivative, and LiMn
2O
4And doping or surface coated derivative) density, can reduce the energy density of lithium rechargeable battery.
As a kind of improvement of lithium ion secondary battery positive electrode pole piece of the present invention, the lithium phosphate in the described anodal diaphragm is an aggregate, and its median diameter is about 10 μ m.
As a kind of improvement of lithium ion secondary battery positive electrode pole piece of the present invention, described plus plate current-collecting body is the aluminium alloy collector.
As a kind of improvement of lithium ion secondary battery positive electrode pole piece of the present invention, contain positive active material in the described anodal diaphragm, positive active material can be transition metal oxide LiNi
0.5Mn
1.5O
2, LiCoO
2, LiMn
2O
4, LiNiCoO
2, LiNiO
2Or the oxide after its other doped with metal elements of process or the coating.
Description of drawings
Below in conjunction with the drawings and specific embodiments, lithium ion secondary battery positive electrode pole piece of the present invention and useful technique effect thereof are elaborated.
Fig. 1 is the structural representation of lithium ion secondary battery positive electrode pole piece of the present invention.
Fig. 2 is that comparative example lithium rechargeable battery and the lithium rechargeable battery that adopts each embodiment of lithium ion secondary battery positive electrode pole piece of the present invention are under normal temperature 4.35V, with the cyclic curve figure of 1C charging 1C discharge.
Embodiment
Comparative example
The preparation of anode pole piece: with lithium cobalt oxygen (LiCoO
2), conductive carbon powder (Super-P), Kynoar (PVDF) mix by weight 97:1.0:2.0, adds N, the anode sizing agent that N-dimethyl pyrrolidone (NMP) mixing and stirring obtains having certain flowability; Then, anode sizing agent is coated on the two sides of 1145 thick aluminium alloy aluminium foils of 16 μ m, coating weight is 0.266g/1540.25mm
2, the anode pole piece with certain suppleness is made in oven dry; At last, respectively through colding pressing, itemize, the positive pole ear made from the aluminium flake of 4x0.1mm is welded on the aluminium foil again, makes anode pole piece.
The preparation of cathode pole piece: with graphite A1, conductive carbon powder (Super-P), sodium carboxymethylcellulose (CMC), butadiene-styrene rubber (SBR) emulsion add mixing and stirring in the deionized water, the cathode size that obtains having certain flowability by weight 96.5:1.0:1.0:1.5; Then, cathode size is uniformly coated on the two sides of the thick metal copper foil of 9 μ m, coating weight is 0.128g/1540.25mm
2, the cathode pole piece with certain suppleness is made in oven dry; At last, process is colded pressing, itemize, after the negative lug made from the nickel sheet of 4x0.1mm is welded on the Copper Foil again, makes cathode pole piece.
The preparation of lithium rechargeable battery: will be that to make model be 606268 liquid flexible packing lithium ion secondary cell with naked electric core by coiling for the barrier film of F20BMU according to anode pole piece, cathode pole piece and the Tonen company model of aforementioned prepared, then through closedtop, side seal, vacuumize, notes electrolyte, Vacuum Package, change into and technology such as ageing, make the finished product lithium rechargeable battery.
Embodiment 1
The preparation of anode pole piece: with lithium cobalt oxygen (LiCoO
2), conductive carbon powder (Super-P), Kynoar (PVDF), lithium phosphate (Li
3PO
4) mix by weight 96.9:1.0:2.0:0.1, add N, the anode sizing agent that N-dimethyl pyrrolidone (NMP) mixing and stirring obtains having certain flowability; Then, anode sizing agent is coated on 1145 thick aluminium alloy aluminium foil two sides of 16 μ m, coating weight is 0.266g/1540.25mm
2, the anode pole piece with certain suppleness is made in oven dry; At last, respectively through colding pressing, itemize, the positive pole ear made from the aluminium flake of 4x0.1mm is welded on the aluminium foil again, makes anode pole piece.
The preparation of cathode pole piece: with graphite A1, conductive carbon powder (Super-P), carboxymethyl cellulose (CMC), SBR emulsion add mixing and stirring in the deionized water, the cathode size that obtains having certain flowability by weight 96.5:1.0:1.0:1.5; Then, cathode size is uniformly coated on the two sides of the thick metal copper foil of 9 μ m, coating weight is 0.128g/1540.25mm
2, be dried into cathode pole piece with certain suppleness; At last, process is colded pressing, itemize, after the negative lug made from the nickel sheet of 4x0.1mm is welded on the Copper Foil again, makes cathode pole piece.
The preparation of lithium rechargeable battery: will be that to make model be 606268 liquid flexible packing lithium ion secondary cell with naked electric core by coiling for the barrier film of F20BMU according to anode pole piece, cathode pole piece and the Tonen company model of aforementioned prepared, then through closedtop, side seal, vacuumize, notes electrolyte, Vacuum Package, change into and technology such as ageing, make the finished product lithium rechargeable battery.
Embodiment 2
The preparation of anode pole piece: with lithium cobalt oxygen (LiCoO
2), conductive carbon powder (Super-P), Kynoar (PVDF), lithium phosphate (Li
3PO
4) mix by weight 96.5:1.0:2.0:0.5, add N, the anode sizing agent that N-dimethyl pyrrolidone (NMP) mixing and stirring obtains having certain flowability; Then, anode sizing agent is coated on 1145 thick aluminium alloy aluminium foil two sides of 16 μ m, coating weight is 0.266g/1540.25mm
2, the anode pole piece with certain suppleness is made in oven dry; At last, respectively through colding pressing, itemize, the positive pole ear made from the aluminium flake of 4x0.1mm is welded on the aluminium foil again, makes anode pole piece.
The preparation of cathode pole piece: with graphite A1, conductive carbon powder (Super-P), carboxymethyl cellulose (CMC), SBR emulsion add mixing and stirring in the deionized water, the cathode size that obtains having certain flowability by weight 96.5:1.0:1.0:1.5; Then, cathode size is uniformly coated on the two sides of the thick metal copper foil of 9 μ m, coating weight is 0.128g/1540.25mm
2, be dried into cathode pole piece with certain suppleness; At last, process is colded pressing, itemize, after the negative lug made from the nickel sheet of 4x0.1mm is welded on the Copper Foil again, makes cathode pole piece.
The preparation of lithium rechargeable battery: will be that to make model be 606268 liquid flexible packing lithium ion secondary cell with naked electric core by coiling for the barrier film of F20BMU according to anode pole piece, cathode pole piece and the Tonen company model of aforementioned prepared, then through closedtop, side seal, vacuumize, notes electrolyte, Vacuum Package, change into and technology such as ageing, make the finished product lithium rechargeable battery.
Embodiment 3
The preparation of anode pole piece: with lithium cobalt oxygen (LiCoO
2), conductive carbon powder (Super-P), Kynoar (PVDF), lithium phosphate (Li
3PO
4) mix by weight 95.0:1.0:2.0:2.0, add N, the anode sizing agent that N-dimethyl pyrrolidone (NMP) mixing and stirring obtains having certain flowability; Then, anode sizing agent is coated on 1145 thick aluminium alloy aluminium foil two sides of 16 μ m, coating weight is 0.266g/1540.25mm
2, the anode pole piece with certain suppleness is made in oven dry; At last, respectively through colding pressing, itemize, the positive pole ear made from the aluminium flake of 4x0.1mm is welded on the aluminium foil again, makes anode pole piece.
The preparation of cathode pole piece: with graphite A1, conductive carbon powder (Super-P), carboxymethyl cellulose (CMC), SBR emulsion add mixing and stirring in the deionized water, the cathode size that obtains having certain flowability by weight 96.5:1.0:1.0:1.5; Then, cathode size is uniformly coated on the two sides of the thick metal copper foil of 9 μ m, coating weight is 0.128g/1540.25mm
2, be dried into cathode pole piece with certain suppleness; At last, process is colded pressing, itemize, after the negative lug made from the nickel sheet of 4x0.1mm is welded on the Copper Foil again, makes cathode pole piece.
The preparation of lithium rechargeable battery: will be that to make model be 606268 liquid flexible packing lithium ion secondary cell with naked electric core by coiling for the barrier film of F20BMU according to anode pole piece, cathode pole piece and the Tonen company model of aforementioned prepared, then through closedtop, side seal, vacuumize, notes electrolyte, Vacuum Package, change into and technology such as ageing, make the finished product lithium rechargeable battery.
Embodiment 4
The preparation of anode pole piece: with lithium cobalt oxygen (LiCoO
2), conductive carbon powder (Super-P), Kynoar (PVDF), lithium phosphate (Li
3PO
4) mix by weight 93.0:1.0:2.0:5.0, add N, the anode sizing agent that N-dimethyl pyrrolidone (NMP) mixing and stirring obtains having certain flowability; Then, anode sizing agent is coated on 1145 thick aluminium alloy aluminium foil two sides of 16 μ m, coating weight is 0.266g/1540.25mm
2, the anode pole piece with certain suppleness is made in oven dry; At last, respectively through colding pressing, itemize, the positive pole ear made from the aluminium flake of 4x0.1mm is welded on the aluminium foil again, makes anode pole piece.
The preparation of cathode pole piece: with graphite A1, conductive carbon powder (Super-P), carboxymethyl cellulose (CMC), SBR emulsion add mixing and stirring in the deionized water, the cathode size that obtains having certain flowability by weight 96.5:1.0:1.0:1.5; Then, cathode size is uniformly coated on the two sides of the thick metal copper foil of 9 μ m, coating weight is 0.128g/1540.25mm
2, be dried into cathode pole piece with certain suppleness; At last, process is colded pressing, itemize, after the negative lug made from the nickel sheet of 4x0.1mm is welded on the Copper Foil again, makes cathode pole piece.
The preparation of lithium rechargeable battery: will be that to make model be 606268 liquid flexible packing lithium ion secondary cell with naked electric core by coiling for the barrier film of F20BMU according to anode pole piece, cathode pole piece and the Tonen company model of aforementioned prepared, then through closedtop, side seal, vacuumize, notes electrolyte, Vacuum Package, change into and technology such as ageing, make the finished product lithium rechargeable battery.
Fig. 1 is the structural representation of lithium ion secondary battery positive electrode pole piece 10 of the present invention, and it comprises plus plate current-collecting body 20 and attached to the anodal diaphragm 30 on the plus plate current-collecting body 20.Anodal diaphragm 30 contains positive active material and the lithium phosphate that is evenly distributed in the anodal diaphragm 30, and positive active material can be a transition metal oxide, as LiCoO
2, LiNi
0.5Mn
1.5O
2, LiMn
2O
4, LiNiCoO
2, LiNiO
2And, also can be the oxide after O (oxygen) is replaced by F (fluorine) through the oxide after other doped with metal elements or the coating.In addition, it is pointed out that in each embodiment of the present invention, lithium phosphate is a kind of aggregate, its median diameter is about 10 μ m (median diameter is meant that the volume that records with laser particle size analyzer is accumulated as 50% o'clock particle diameter), and the granularity of its primary particle is≤1 μ m.
Fig. 2 is that comparative example lithium rechargeable battery and the lithium rechargeable battery that adopts each embodiment of lithium ion secondary battery positive electrode pole piece of the present invention are under normal temperature 4.35V, with the cyclic curve figure of 1C charging 1C discharge.As can be seen from the figure: the cycle performance of lithium rechargeable battery that adopts each embodiment of lithium ion secondary battery positive electrode pole piece of the present invention is significantly better than the cycle performance of comparative example lithium rechargeable battery, wherein, the cycle performance of the lithium rechargeable battery of embodiment 3 and embodiment 4 correspondences rises to the capability retention of 300 circulations 80% and the capability retention of 300 circulations 87% respectively by the capability retention of 80 circulations 80% of comparative example, therefore, can significantly improve cycle performance under the lithium rechargeable battery high potential.
Need to prove, the announcement of book and elaboration according to the above description, those skilled in the art in the invention can also change and revise above-mentioned execution mode.Therefore, the embodiment that discloses and describe above the present invention is not limited to also should be in the protection range of claim of the present invention to equivalent modifications more of the present invention and change.In addition, although used some specific terms in this specification, these terms do not constitute any restriction to the present invention just for convenience of description.
Claims (5)
1. lithium ion secondary battery positive electrode pole piece, it comprises plus plate current-collecting body and attached to the anodal diaphragm on the plus plate current-collecting body, it is characterized in that: contain equally distributed lithium phosphate in the described anodal diaphragm.
2. lithium ion secondary battery positive electrode pole piece according to claim 1 is characterized in that: in the described anodal diaphragm, the weight content of lithium phosphate is 0.1% to 5.0%.
3. lithium ion secondary battery positive electrode pole piece according to claim 1 is characterized in that: the lithium phosphate in the described anodal diaphragm is an aggregate, and its median diameter is about 10 μ m.
4. lithium ion secondary battery positive electrode pole piece according to claim 1 is characterized in that: described plus plate current-collecting body is the aluminium alloy collector.
5. according to each described lithium ion secondary battery positive electrode pole piece in the claim 1 to 4, it is characterized in that: contain positive active material in the described anodal diaphragm, positive active material can be transition metal oxide LiCoO
2, LiNi
0.5Mn
1.5O
2, LiMn
2O
4, LiNiCoO
2, LiNiO
2Or the oxide after its other doped with metal elements of process or the coating.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010105951927A CN102064314A (en) | 2010-12-20 | 2010-12-20 | Anode piece of lithium ion secondary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010105951927A CN102064314A (en) | 2010-12-20 | 2010-12-20 | Anode piece of lithium ion secondary battery |
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| CN102064314A true CN102064314A (en) | 2011-05-18 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105431971A (en) * | 2013-05-16 | 2016-03-23 | 丰田自动车株式会社 | Electrode paste production method |
| CN117393768A (en) * | 2023-12-11 | 2024-01-12 | 天鹏锂能技术(淮安)有限公司 | Positive electrode material for sodium ion battery, preparation method of positive electrode material and sodium ion battery |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005302338A (en) * | 2004-04-07 | 2005-10-27 | Shin Kobe Electric Mach Co Ltd | Lithium secondary battery and positive electrode material for lithium secondary battery |
| CN101257133A (en) * | 2007-02-27 | 2008-09-03 | 三洋电机株式会社 | Non-aqueous electrolyte secondary battery |
| CN101841066A (en) * | 2009-03-16 | 2010-09-22 | 三洋电机株式会社 | Nonaqueous electrolytic solution secondary battery |
-
2010
- 2010-12-20 CN CN2010105951927A patent/CN102064314A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005302338A (en) * | 2004-04-07 | 2005-10-27 | Shin Kobe Electric Mach Co Ltd | Lithium secondary battery and positive electrode material for lithium secondary battery |
| CN101257133A (en) * | 2007-02-27 | 2008-09-03 | 三洋电机株式会社 | Non-aqueous electrolyte secondary battery |
| CN101841066A (en) * | 2009-03-16 | 2010-09-22 | 三洋电机株式会社 | Nonaqueous electrolytic solution secondary battery |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105431971A (en) * | 2013-05-16 | 2016-03-23 | 丰田自动车株式会社 | Electrode paste production method |
| CN105431971B (en) * | 2013-05-16 | 2017-12-22 | 丰田自动车株式会社 | The manufacture method of electrode paste agent |
| US9853282B2 (en) | 2013-05-16 | 2017-12-26 | Toyota Jidosha Kabushiki Kaisha | Electrode paste production method |
| CN117393768A (en) * | 2023-12-11 | 2024-01-12 | 天鹏锂能技术(淮安)有限公司 | Positive electrode material for sodium ion battery, preparation method of positive electrode material and sodium ion battery |
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Application publication date: 20110518 |