CN102280641A - Secondary lithium battery and cathode sheet thereof - Google Patents
Secondary lithium battery and cathode sheet thereof Download PDFInfo
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- CN102280641A CN102280641A CN2011101735251A CN201110173525A CN102280641A CN 102280641 A CN102280641 A CN 102280641A CN 2011101735251 A CN2011101735251 A CN 2011101735251A CN 201110173525 A CN201110173525 A CN 201110173525A CN 102280641 A CN102280641 A CN 102280641A
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- negative electrode
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- antiacid
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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 a cathode sheet used in a secondary lithium battery. The cathode sheet comprises a current collector and a cathode film attached to the surface of the current collector. The cathode film contains a nano-sized antiacid, wherein the content of the antiacid in the cathode film is 0.5 wt% to 2.5 wt%. Compared to prior arts, the antiacid is added to the cathode film, such that the generation of HF in an electrolyte can be reduced; added alkaline substances such as MgO and Mg(OH)2 are effectively subject to a reaction with HF generated from the electrolyte, such that dissolving and corroding of transition metal ions in cathode active substances are reduced, and the structures of the cathode active substances can be maintained. Therefore, circulation performance of the lithium battery can be improved. Also, the invention discloses a secondary lithium battery with the cathode sheet.
Description
Technical field
The present invention relates to the serondary lithium battery technical field, relate in particular to serondary lithium battery and negative electrode pole piece thereof with good circulation performance.
Background technology
In recent years, serondary lithium battery is because of its energy density height, and the voltage height, self-discharge rate is low and the market share of advantage in miniaturized electronicss such as digital camera, notebook computer such as in light weight increases sharply; But it is, more and more higher to the requirement in useful life of battery along with the enhancing of people to bad border and protection of resources consciousness.
Mainly concentrate on surface coating/doping, the electrolysis additive aspect of cathode active material at present in the research aspect the raising secondary cell cycle life.For example, notification number be 100385712C patent disclosure a kind of at LiNi
xCo
1-xO
2The surface doping of (0＜x＜1) coats the cathode material for lithium ion battery of layer of metal oxide, and metal oxide is Al
2O
3, MgO or Al, the mixed oxide of Mg etc.By coating, can avoid cathode active material and the direct of electrolyte to contact, improved the cycle performance of material to a certain extent, but the process need that coats carries out high temperature sintering, complicated operation, cost height.
Document J.Electrochem.Soc., Vol.140, No.6, L101 (1993) have put down in writing and provide a kind of is the main component of electrolyte with PC, EC, adds crown compound (12-crown-4), with the decomposition of inhibition electrolyte, thus the scheme of raising cycle performance.But crown ether costs an arm and a leg, even a large amount of the adding, the effect that suppresses electrolyte decomposition is also little, and the battery behavior that reaches is not remarkable yet.
Publication number is that the Chinese patent of 101388474A discloses and a kind ofly adds alkaline matter in the negative electrode LiMn2O4, and adds the scheme that LiBOB improves the cycle performance of lithium manganate battery in electrolyte.But the alkaline matter particle is bigger, can not realize evenly fully disperseing, and along with the increase of period, it is to the DeGrain that improves of the circulation of battery, and LiBOB solubility in the solvent of low-k is very low, can influence the capacity performance of battery.
In view of this, necessary a kind of cheap serondary lithium battery that can significantly improve the lithium battery cycle performance and the negative electrode pole piece thereof of providing.
Summary of the invention
The objective of the invention is to:, and provide a kind of production cost the low serondary lithium battery that can significantly improve lithium battery cycle performance negative electrode pole piece at the deficiencies in the prior art.
In order to achieve the above object, the present invention adopts following technical scheme:
A kind of serondary lithium battery negative electrode pole piece comprises collector and attached to the negative electrode diaphragm of collection liquid surface, contains the nanometer antiacid in the described negative electrode diaphragm that the content of described nanometer antiacid in the negative electrode diaphragm is 0.5wt%～2.5wt%.Select for use the nanometer antiacid to be because nanoparticle size is little, can be in the negative electrode diaphragm evenly disperse, to greatest extent with circulation in the HF reaction that produces, improve the cycle performance of lithium battery.When its content during,, thereby the energy density of the cycle performance of battery, big multiplying power discharging property and battery all there is negative effect because these nanometer antiacid poorly conductives cause the resistance of pole piece excessive greater than 2.5wt%.
As a kind of improvement of serondary lithium battery of the present invention with the negative electrode pole piece, described nanometer antiacid is nano-MgO or nanometer Mg (OH)
2Because they can catch HF, form MgF
2, MgF
2Form hydrate with H2O, prevented the dissolved corrosion of HF, thereby play the effect of protection negative electrode transition metal ions in the positive active material.Reaction equation: 2HF+MgO → MgF
2+ H2O, 2HF+Mg (OH) 2 → MgF2+2H2O
As a kind of improvement of serondary lithium battery of the present invention with the negative electrode pole piece, described nanometer antiacid is nano-MgO and nanometer Mg (OH)
2
As a kind of improvement of serondary lithium battery of the present invention with the negative electrode pole piece, the content of described nanometer antiacid in the negative electrode diaphragm is 1.0wt%～2.5wt%.
As a kind of improvement of serondary lithium battery of the present invention with the negative electrode pole piece, the content of described nanometer antiacid in the negative electrode diaphragm is 2.5wt%.
Relative prior art, the present invention can reduce the amount that HF produces in the electrolyte, MgO that is added and Mg (OH) on the other hand on the one hand effectively by add the nanometer antiacid in the negative electrode diaphragm
2Can be effectively and the HF that generates in electrolyte reaction Deng alkaline matter, reduced the dissolved corrosion of transition metal ions in the cathode active material, help keeping the structure of cathode active material, thereby improve the cycle performance of lithium battery.In addition, the present invention only needs to add the acid of nanometer antioxygen in the negative electrode diaphragm, need not pass through high temperature sintering, also need not to add additive in electrolyte, has saved production cost.
Another purpose of the present invention is: a kind of serondary lithium battery with good circulation performance is provided, it negative electrode diaphragm, anode collector that comprises that cathode current collector reaches attached to the cathode collector surface reaches anode diaphragm, electrolyte, barrier film and external packing attached to the anode current collector surface, and described negative electrode diaphragm is the described negative electrode diaphragm of above-mentioned paragraph.
As a kind of improvement of serondary lithium battery of the present invention, the active material in the described negative electrode diaphragm is lithium nickel cobalt manganese oxygen (LiNiCoMnO
2), lithium manganese oxygen (LiMn
2O
4), in cobalt acid lithium or the LiFePO 4 any one or multiple.
Description of drawings
Below in conjunction with the drawings and specific embodiments, the present invention and useful technique effect thereof are described in detail, wherein:
Fig. 1 is the comparison diagram of serondary lithium battery of the present invention and the cycle performance curve of common serondary lithium battery (the negative electrode diaphragm does not contain the nanometer antiacid) under 45 ℃.
Embodiment
Used antiacid MgO and Mg (OH) in the embodiments of the invention
2Median diameter be about 10nm (median diameter is meant that the volume that records with laser particle size analyzer is accumulated as 50% o'clock particle diameter).
Embodiment 1
Anode pole piece preparation: with LiNiCoMnO
2(lithium nickel cobalt manganese oxygen), LiMn
2O
4(lithium manganese oxygen), Super-P (electric conducting material), PVDF: MgO were according to mass ratio 57%: 38%: 2.2%: add the slurry that mixing and stirring obtains having certain flowability in the deionized water at 2.3%: 0.5%, above-mentioned slurry is coated on the aluminium foil two sides of the thick aluminium alloy of 20um numbers 1145, coating weight is 0.283g/1540.25mm again
2, be dried into anode pole piece with certain suppleness, then respectively through colding pressing, itemize, the positive pole ear made from the aluminium flake of 4*0.1mm is welded on and makes anode pole piece on the aluminium foil again.
The preparation of cathode pole piece: with graphite, Super-P (conductive carbon powder), CMC, SBR emulsion are 95.2%: 1.5%: 1.0% according to mass ratio: mix and stir obtaining having the slurry of certain flowability in the 2.3% adding deionized water, above-mentioned slurry is coated on the two sides of the thick metal copper foil of 9um, coating weight is 0.120g/1540.25mm again
2, be dried into cathode pole piece with certain suppleness, then through colding pressing, itemize, after the negative lug made from the nickel sheet of 4*0.1mm is welded on the Copper Foil, make cathode pole piece.
The preparation of battery: the anode pole piece that makes and cathode pole piece and F20BMU (20um) barrier film are made 606268 by coiling (longly be 68mm, wide is 62mm, thick is 6.0mm) naked electric core, then through closedtop, side seal, vacuumize, notes electrolyte, Vacuum Package, change into, technology such as ageing, make the finished product battery.
The cycle performance test: charge and discharge cycles test multiplying power is 0.7C/0.5C, and discharging and recharging cut-ff voltage is 4.2V/3.0V.
Embodiment 2
The present embodiment difference from Example 1 is, LiNiCoMnO
2(lithium nickel cobalt manganese oxygen), Super-P (electric conducting material), PVDF: Mg (OH) 2 mass ratios are 94%: 2.2%: 2.3%: 1.5%, and all the other are with embodiment 1.
Embodiment 3
The present embodiment difference from Example 1 is, LiMn
2O
4(lithium manganese oxygen), Super-P (electric conducting material), PVDF: the MgO mass ratio is 94%: 2.2%: 2.3%: 1.5%: all the other are with embodiment 1.
Embodiment 4
The present embodiment difference from Example 1 is, LiMn
2O
4(lithium manganese oxygen), Super-P (electric conducting material), PVDF: MgO: Mg (OH)
2Mass ratio is 93%: 2.2%: 2.3%: 1.5%: 1%, all the other were with embodiment 1.
Comparative Examples
This Comparative Examples is LiNiCoMnO with the difference of embodiment 1
2(lithium nickel cobalt manganese oxygen), LiMn
2O
4(lithium manganese oxygen), Super-P (electric conducting material), PVDF mass ratio are 57.3%: 38.2%: 2.2%: 2.3%, and all the other are with embodiment 1.
The capability retention of 45 ℃ of following 300 circulations of embodiment is as table-1, from table-1 as can be seen: add the capability retention that the nanometer antiacid has obviously improved 45 ℃ of circulations the negative electrode.Because the introducing of nanometer antiacid, effectively reduced the amount that HF produces in the electrolyte on the one hand, the nanometer antiacid that is added on the other hand can effectively and produce the HF reaction in the electrolyte, reduced the dissolving of transition metal ions in the HF target active material, help the maintenance of cathode active material structure, thereby improved the cycle performance of battery.Along with the 2.5wt% that the content of nanometer antiacid is improved by 1wt%, the capability retention of 300 circulations is improved by 85.4% of Comparative Examples brings up to 88.2% and 93.1% respectively.
Table-1: the capability retention of 45 ℃ of following 300 circulations of embodiment and Comparative Examples
| 300 circulation volume conservation rate _ 45 ℃ cycle | |
| Comparative Examples | 85.4％ |
| Embodiment 1 | 88.2％ |
| Embodiment 2 | 90.0％ |
| Embodiment 3 | 90.0％ |
| Embodiment 4 | 93.1％ |
Embodiment 5
The present embodiment difference from Example 1 is, active material in the described negative electrode diaphragm is cobalt acid lithium, Super-P (electric conducting material), PVDF: the MgO mass ratio is 94.2%: 2.0%: 2.3%: 1.5%, other are identical with embodiment 1, no longer repeat here.
Compare with the battery that does not add MgO, 45 ℃ of cycle performances of the battery of embodiment 5 are significantly improved, and it is 94% that the capability retention of 400 circulations promotes by 85%.
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 (6)
1. serondary lithium battery negative electrode pole piece, comprise collector and attached to the negative electrode diaphragm of collection liquid surface, it is characterized in that: contain the nanometer antiacid in the described negative electrode diaphragm, the content of described nanometer antiacid in the negative electrode diaphragm is 0.5wt%～2.5wt%.
2. serondary lithium battery negative electrode pole piece according to claim 1 is characterized in that: described nanometer antiacid is nano-MgO or nanometer Mg (OH)
2
3. serondary lithium battery negative electrode pole piece according to claim 1 is characterized in that: described nanometer antiacid is nano-MgO and nanometer Mg (OH)
2
4. serondary lithium battery negative electrode pole piece according to claim 1 is characterized in that: the content of described nanometer antiacid in the negative electrode diaphragm is 1.0wt%～2.5wt%.
5. serondary lithium battery, comprise that negative electrode diaphragm, anode collector that cathode current collector reaches attached to the cathode collector surface reach anode diaphragm, electrolyte, barrier film and external packing attached to the anode current collector surface, it is characterized in that: described negative electrode diaphragm is each described negative electrode diaphragm in the claim 1 to 4.
6. serondary lithium battery according to claim 5 is characterized in that: the active material in the described negative electrode diaphragm is lithium nickel cobalt manganese oxygen (LiNiCoMnO
2), lithium manganese oxygen (LiMn
2O
4), in cobalt acid lithium or the LiFePO 4 any one.
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|---|---|---|---|
| CN2011101735251A CN102280641A (en) | 2011-06-27 | 2011-06-27 | Secondary lithium battery and cathode sheet thereof |
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|---|---|---|---|
| CN2011101735251A CN102280641A (en) | 2011-06-27 | 2011-06-27 | Secondary lithium battery and cathode sheet thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103633328A (en) * | 2012-08-24 | 2014-03-12 | 中国科学院上海微系统与信息技术研究所 | Lithium ion battery ternary positive plate containing weakly-alkaline metallic compound and manufacturing method thereof |
| CN104882610A (en) * | 2014-02-27 | 2015-09-02 | 奇瑞汽车股份有限公司 | Li-Ni-Mn-O lithium ion battery pole piece and battery |
| CN106340637A (en) * | 2015-07-07 | 2017-01-18 | 中国科学院成都有机化学有限公司 | Polysilicate/NCM three-component composite positive electrode material for lithium ion battery and preparation method thereof |
Citations (3)
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|---|---|---|---|---|
| CN101325254A (en) * | 2008-07-15 | 2008-12-17 | 长沙杉杉动力电池有限公司 | Method for manufacturing positive plate of iron phosphate lithium battery |
| CN101388474A (en) * | 2008-11-07 | 2009-03-18 | 中南大学 | Lithium manganate cell |
| CN101950803A (en) * | 2010-05-17 | 2011-01-19 | 东莞新能源科技有限公司 | Preparation method of cathode material of lithium ion battery coated with metal oxides on surface |
-
2011
- 2011-06-27 CN CN2011101735251A patent/CN102280641A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101325254A (en) * | 2008-07-15 | 2008-12-17 | 长沙杉杉动力电池有限公司 | Method for manufacturing positive plate of iron phosphate lithium battery |
| CN101388474A (en) * | 2008-11-07 | 2009-03-18 | 中南大学 | Lithium manganate cell |
| CN101950803A (en) * | 2010-05-17 | 2011-01-19 | 东莞新能源科技有限公司 | Preparation method of cathode material of lithium ion battery coated with metal oxides on surface |
Non-Patent Citations (2)
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|---|
| SUNG BIN PARK: "An alternative method to improve the electrochemical performace of a lithium secondary battery with LiMn2O4", 《JOURNALOF POWER SOURCES》 * |
| SUNG BIN PARK: "An alternative method to improve the electrochemical performance of a lithium secondary battery with LiMn2O4", 《JOURNAL OR POWER SOURCES》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103633328A (en) * | 2012-08-24 | 2014-03-12 | 中国科学院上海微系统与信息技术研究所 | Lithium ion battery ternary positive plate containing weakly-alkaline metallic compound and manufacturing method thereof |
| CN104882610A (en) * | 2014-02-27 | 2015-09-02 | 奇瑞汽车股份有限公司 | Li-Ni-Mn-O lithium ion battery pole piece and battery |
| CN106340637A (en) * | 2015-07-07 | 2017-01-18 | 中国科学院成都有机化学有限公司 | Polysilicate/NCM three-component composite positive electrode material for lithium ion battery and preparation method thereof |
| CN106340637B (en) * | 2015-07-07 | 2020-07-03 | 成都市博伦沃德新能源科技有限公司 | polysilicate/NCM ternary composite cathode material for lithium ion battery and preparation method thereof |
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Application publication date: 20111214 |