CN208674263U - Compound cathode and lithium secondary battery - Google Patents
Compound cathode and lithium secondary battery Download PDFInfo
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- CN208674263U CN208674263U CN201821400387.XU CN201821400387U CN208674263U CN 208674263 U CN208674263 U CN 208674263U CN 201821400387 U CN201821400387 U CN 201821400387U CN 208674263 U CN208674263 U CN 208674263U
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- lithium
- secondary battery
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- band
- compound cathode
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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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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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Abstract
Provide a kind of compound cathode and the lithium secondary battery including the cathode.The compound cathode includes the five layers of composite construction formed by collector, the lithium band positioned at collector two sides or lithium alloy band and between collector and lithium band or lithium alloy band and with the carbon layer that they are directly contacted.
Description
Technical field
The utility model relates to the field of secondary cell more particularly to a kind of simply compound cathode of preparation process and make
With the secondary cell of the cathode.
Background technique
In recent years, as the electric equipment products such as smart phone, tablet computer, electric car are to the need of high-energy electrochmical power source
It asks and petroleum coal resources non-renewable and pollution that combusts fossil resource is to environment, the secondary cell of high-energy density
It has become a hot topic of research.At present using graphite as cathode, LiFePO4, cobalt acid lithium, ternary material etc. are the secondary cell of anode
Specific energy development space is limited, almost limiting value.In lithium secondary battery, lithium metal have most negative electrode potential (-
3.045V) with highest specific capacity (3860mAh/g), it is able to satisfy the requirement of electrode material high-energy density, lot of domestic and international section
It grinds institutes and company turns to using lithium as the research and development of the secondary cell of cathode and application.
Utility model content
Present inventor is being dedicated to using the research of lithium band or lithium alloy band as lithium secondary battery cathode material
Two kinds of metal material direct pressures are combined with each other by middle discovery although generally believing, good between the two connect may be implemented
Touching and bonding, but work as using lithium band or lithium alloy band as negative electrode material direct combination on metal collector (such as copper foil)
When, it is possible to there are some places to bond not tight phenomenon, causes conduction electronic capability between negative electrode material and collector weak, boundary
Face impedance is big, and the capacity of battery reduces.
To solve the above-mentioned problems, inventor has made intensive studies, as a result, it has been found that: by using laminated composite structure,
That is, first forming carbon layer (especially containing the carbon layer of porous carbon material) on metal collector surface, then compound on it
Adhesiveness and electronics conduction energy between lithium band or lithium alloy band and metal collector not only can be improved in lithium band or lithium alloy band
Power, and the growth of Li dendrite can be inhibited, improve the capacity retention ratio of battery.
The one aspect of the utility model provides a kind of compound cathode, and the cathode includes by collector, is located at afflux
The lithium band or lithium alloy band of body two sides and the carbonaceous directly contacted between collector and lithium band or lithium alloy band and with them
Five layers of composite construction that layer is formed.
The other side of the utility model provides a kind of secondary cell comprising above-mentioned cathode, the preferably lithium
Secondary cell is lithium-sulfur cell, lithium-air battery, lithium polymer battery or lithium all-solid-state battery.
According to the utility model, carbon layer, the carbon layer are provided between lithium band or lithium alloy band and metal collector
Electronic conduction ability can be improved while guaranteeing adhesiveness between lithium band or lithium alloy band and metal collector, especially existed
In the case where porous carbon material, the large specific surface area of porous carbon material increases the deposition site of lithium ion, reduces
Effective current density effectively inhibits the growth of Li dendrite, improves chemical property.
Detailed description of the invention
Fig. 1 shows the front view of the secondary battery negative pole of an embodiment according to the present utility model
Sectional view of the coiled cathode along line A-A that Fig. 2 is Fig. 1.
Fig. 3 shows the secondary cell cycle performance test chart of embodiment 1,2 and 3.
Specific embodiment
Fig. 1 shows the front view of the compound cathode of an embodiment according to the present utility model.The cathode be at
Roll form, and be collector two sides complex form, that is, there is carbon layer 2 on the two sides of collector 3；Carbon layer 2 it is two-sided compound
Lithium band or lithium alloy band 1.
Sectional view of the coiled cathode along line A-A that Fig. 2 is Fig. 1.It should be pointed out that lithium band or lithium alloy in Fig. 1 and Fig. 2
Width with 1, carbon layer 2 and collector 3 can arbitrarily be changed, not necessarily in ratio in figure, under normal circumstances, lithium band or lithium alloy
The width of band and carbon layer can be slightly narrower than the width of collector.
Negative electrode active material is lithium metal or lithium alloy in the utility model, is mentioned in the form of metal lithium bands or lithium alloy band
For.The thickness of metal lithium bands or lithium alloy band can be 0.02-0.20mm, preferably 20-50um.Lithium alloy is by lithium metal and extremely
A kind of few other elements are constituted, and the other elements may include: magnesium, boron, aluminium, silicon, indium, zinc, silver, calcium, manganese element.It is described its
The content of his element accounts for the 0.1%~40% of lithium alloy gross mass, preferably 1%~20%.
The collector of the utility model includes metal foil, foam metal, preferably copper foil, nickel foil, foam copper and nickel foam
At least one of.Metal foil, such as the thickness of copper foil can be 6~10 microns.The thickness of foam metal can for 0.1~
0.5mm.The width of collector can be 10-3000mm.
The carbon layer of the utility model may include micron order or nanoscale conductive carbon particle.Conductive carbon particle can select
Select carbon black, graphite, acetylene black, Ketjen black, active carbon, activated carbon fiber, mesoporous carbon, carbon nanotube, carbon molecular sieve, in graphene
At least one.It is preferred that porous, electrically conductive carbon particle comprising active carbon, activated carbon fiber, mesoporous carbon, carbon nanotube microballoon, carbon
Molecular sieve, carbon nano-fiber, carbon hollow nano-sphere, hollow carbon balls at least one.Preferably, the aperture of porous, electrically conductive carbon particle
Magnitude range is 0.1~100nm, preferably 0.1nm~20nm.Carbon layer single side is with a thickness of 0.5~5um.The single side face of carbon layer
Density is 0.5-1.5g/m2。
In the utility model, carbon layer can be formed in the two sides of collector by rubbing method or by vapour deposition process
On.For example, slurry can be mixed in a certain ratio by porous, electrically conductive carbon particle, binder and solvent, it is applied to afflux later
On body, carbon layer is formed after curing and drying.Binder can choose Kynoar (PVDF), polytetrafluoroethylene (PTFE) (PTFE),
Butadiene-styrene rubber (SBR), sodium carboxymethylcellulose (CMC) etc.；Solvent can choose N,N-dimethylformamide (DMF), N- methyl
Pyrrolidones (NMP), paraxylene (PX), tetrahydrofuran (THF) etc..The slurry of carbon layer includes following mass percentage
Component: conductive carbon particle 5%-15%, binder 0.1%-0.5%, balance of solvent.
It, can be by the coiled afflux with carbon layer after the two-sided upper formation carbon layer of collector in the utility model
Body and coiled lithium band or lithium alloy band are by winding/unwinding device, using mechanical pressure, by lithium band or lithium alloy band and with carbon
The collector of matter layer is combined to together, can be prepared by secondary battery negative pole.Its manufacturing process is simple, can produce in batches.
The lithium secondary battery of the utility model includes cathode as above, further includes anode, electrolyte, diaphragm and shell.
The anode of the utility model lithium secondary battery includes collector and the two-sided positive electrode material layer for being formed in collector.
Positive electrode material layer is that positive electrode slurry is applied to the two-sided of collector to obtain.
According to some embodiments, anode sizing agent includes positive electrode active materials, conductive agent, binder and solvent.Positive-active
Material includes the active material that can be used for anode of secondary battery in this field, for example, LiFePO4, cobalt acid lithium, nickel cobalt aluminium ternary,
Nickel-cobalt-manganese ternary material, sulphur simple substance, the sulphur simple substance, oxygen, the vanadic anhydride that adulterate conductive agent etc..Conductive agent and binder include
It can be used for the conductive agent and binder of anode of secondary battery in this field, for example, conductive agent may include graphite, graphene, carbon
Nanotube, carbon fiber, conductive carbon black (Super P), acetylene black, Ketjen black etc.；Binder may include Kynoar
(PVDF), polytetrafluoroethylene (PTFE) (PTFE) etc..Solvent may include n-methyl-2-pyrrolidone (NMP) etc..
The plus plate current-collecting body that can be used for the utility model can be plus plate current-collecting body commonly used in the art, such as aluminium foil,
Carbon coating aluminium foil.
The electrolyte that can be used for the utility model secondary cell may include esters, ethers, polymer dielectric, ionic liquid
Body, solid electrolyte etc..Such as: ethylene carbonate, propene carbonate, diethyl carbonate；1,3-dioxolane (DOL), second two
Diethylene glycol dimethyl ether (DME)；Li2S-P2S5Class, Li10GeP2S12, LLZO (lithium lanthanum zirconium oxygen) solid electrolyte, PEO (polyethylene oxide) is poly-
Close species；The cation and imines anion (TFSI of piperidines, pyroles or quaternary ammonium salt-) ionic liquid etc. that is formed.
The diaphragm and shell that can be used for the utility model secondary cell can be diaphragm and shell commonly used in the art, example
Such as, diaphragm can be membrane for polymer, such as polyethylene (PE) film, polypropylene (PP) film, polyethylene-polypropylene-polyethylene
(PE-PP-PE) film etc.；Shell can be the flexible package of laminated film or metal-back packaging.
The secondary cell of the utility model can use stacked or takeup type structure.
Embodiment
Hereinafter, the utility model is more fully described by embodiment, but these embodiments are merely exemplary, without answering
It is interpreted as the limitation to the scope of the utility model.
Embodiment 1
The preparation of copper foil with carbon layer: carbon layer slurry includes the component of following mass percentage: active carbon (hole
Diameter 2.0-2.2nm, lucky storehouse nanometer) 6.5%, binder PVDF (Zhejiang Fluorine Chemical New Material Co., Ltd., similarly hereinafter)
0.2%, solvent NMP (Shanghai Aladdin biochemical technology limited liability company, similarly hereinafter) surplus, magnetic agitation are uniformly mixed, obtain
Uniform carbon pastes.Using automatic coating machine, in coiled copper foil of affluxion body, (Lingbao Wason Copper Foil Co., Ltd., thickness 9 are micro-
Double spread slurry on rice, similarly hereinafter), after curing and drying, single side carbon layer with a thickness of 1 micron, obtain coiled there is carbonaceous
The copper foil of layer.
Cathode preparation: it is protected by winding/unwinding device and lining form, using mechanical pressure with the two-sided of carbon layer copper foil
Compound upper lithium band, lithium tape thickness are 35 microns, obtain cathode.
Anode preparation: positive active material LiFePO is pressed4(Hunan Shanshan New Materials Co., Ltd): artificial graphite (Tianjin
Bei Terui New Energy Technology Co., Ltd.): solvent NMP, mixing is added in the ratio mixing of binder PVDF 8:1:1 in mass ratio
At slurry, it is coated in current collector aluminum foil (sky dragon Aluminum Co., Ltd, Gongyi City, 10 microns of thickness, similarly hereinafter) and is prepared into anode,
80 DEG C of vacuum oven dry 24 hours for use.
Electrolyte selection 1mol/L LiPF6-EC/EMC (volume ratio 1:1, EC: ethylene carbonate, EMC: methyl ethyl carbonate,
Dongguan Shan Shan battery material Co., Ltd)；Diaphragm is PP (polypropylene) diaphragm, is assembled into battery testing chemical property, voltage
Range 3.0-4.2V, with the rate charge-discharge of 0.2C.
Embodiment 2
The preparation of copper foil with carbon layer: carbon layer slurry includes the component of following mass percentage: artificial graphite
6.5%, binder PVDF 0.2%, solvent NMP surplus, magnetic agitation are uniformly mixed, and obtain uniform carbon pastes.Using automatic
Coating machine, the double spread slurry on coiled copper foil of affluxion body, single side carbon layer with a thickness of 1 micron, obtain coiled having
The copper foil of carbon layer.
Cathode preparation: protecting by winding/unwinding device and lining form, using mechanical pressure in the double of the copper foil with carbon layer
The compound upper lithium band in face, lithium tape thickness are 35 microns, obtain cathode.
Positive electrode, electrolyte and diaphragm are consistent with embodiment 1.It is assembled into battery testing chemical property, voltage model
3.0-4.2V is enclosed, with the rate charge-discharge of 0.2C.
Embodiment 3
Cathode preparation: it is protected by winding/unwinding device and lining form, on coiled copper foil of affluxion body (9 microns of thickness) is two-sided
Compound upper lithium band, obtains cathode by 35 microns of lithium tape thickness
Positive electrode, electrolyte and diaphragm are consistent with embodiment 1.It is assembled into battery testing chemical property, voltage model
3.0-4.2V is enclosed, with the rate charge-discharge of 0.2C.
Embodiment 1 and embodiment 2 and 3 cycle performance of embodiment as shown in figure 3, by cycle performance figure can be seen that come,
The embodiment 1 of composite carbonaceous layer and 2 battery performance of embodiment are more preferable on copper foil；Embodiment 1 and embodiment 2 compare, in carbon layer
Performance is more preferable when conductive carbon material uses porous carbon.The specific surface area of porous carbon is very big, reduces effective current density, increases
The deposition site of lithium ion inhibits the generation of Li dendrite.Specific value such as following table one.
Table one
Claims (10)
1. a kind of compound cathode, which is characterized in that the cathode includes by collector, positioned at the lithium band or lithium of collector two sides
Alloy strip and the five-layer structure formed between collector and lithium band or lithium alloy band and with the carbon layer that they are directly contacted.
2. compound cathode according to claim 1, which is characterized in that the lithium band or lithium alloy tape thickness be
0.020-0.20mm。
3. compound cathode according to claim 1, which is characterized in that the single side of the carbon layer with a thickness of 0.5~
5um。
4. compound cathode according to claim 1, which is characterized in that the carbon layer includes micron order or nanoscale
Conductive carbon particle.
5. compound cathode according to claim 4, which is characterized in that the carbon layer includes porous conductive carbon
Grain.
6. compound cathode according to claim 1, which is characterized in that the collector is metal foil or foam gold
Belong to.
7. compound cathode according to claim 6, which is characterized in that the metal foil or foam metal be copper foil,
At least one of nickel foil, foam copper and nickel foam.
8. a kind of lithium secondary battery, which is characterized in that the lithium secondary battery includes of any of claims 1-7
Compound cathode.
9. lithium secondary battery according to claim 8, which is characterized in that the lithium secondary battery is lithium-sulfur cell, lithium
Air cell, lithium polymer battery or lithium all-solid-state battery.
10. lithium secondary battery according to claim 8, which is characterized in that the lithium secondary battery is stacked or volume
It is wound.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201821400387.XU CN208674263U (en) | 2018-08-29 | 2018-08-29 | Compound cathode and lithium secondary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201821400387.XU CN208674263U (en) | 2018-08-29 | 2018-08-29 | Compound cathode and lithium secondary battery |
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| Publication Number | Publication Date |
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| CN208674263U true CN208674263U (en) | 2019-03-29 |
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| CN201821400387.XU Active CN208674263U (en) | 2018-08-29 | 2018-08-29 | Compound cathode and lithium secondary battery |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110875476A (en) * | 2018-08-29 | 2020-03-10 | 天津中能锂业有限公司 | Negative electrode for lithium secondary battery, method for preparing same, and lithium secondary battery |
| WO2022267534A1 (en) * | 2021-06-26 | 2022-12-29 | 宁德时代新能源科技股份有限公司 | Lithium metal negative electrode plate, electrochemical apparatus, and electronic device |
-
2018
- 2018-08-29 CN CN201821400387.XU patent/CN208674263U/en active Active
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110875476A (en) * | 2018-08-29 | 2020-03-10 | 天津中能锂业有限公司 | Negative electrode for lithium secondary battery, method for preparing same, and lithium secondary battery |
| WO2022267534A1 (en) * | 2021-06-26 | 2022-12-29 | 宁德时代新能源科技股份有限公司 | Lithium metal negative electrode plate, electrochemical apparatus, and electronic device |
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