CN109390586A - A kind of cathode expansion the inhibition structure and cathode and preparation method thereof of lithium ion battery - Google Patents
A kind of cathode expansion the inhibition structure and cathode and preparation method thereof of lithium ion battery Download PDFInfo
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- CN109390586A CN109390586A CN201811409358.4A CN201811409358A CN109390586A CN 109390586 A CN109390586 A CN 109390586A CN 201811409358 A CN201811409358 A CN 201811409358A CN 109390586 A CN109390586 A CN 109390586A
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- cathode
- overlength
- conductive agent
- foil
- lithium ion
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/70—Carriers or collectors characterised by shape or form
- H01M4/80—Porous plates, e.g. sintered carriers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- 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
Abstract
It is expanded the present invention provides a kind of cathode of lithium ion battery and inhibits structure and cathode and preparation method thereof, it includes porous copper foil and the linear conductive agent of overlength that the cathode expansion, which inhibits structure, and the linear conductive agent of overlength is interspersed between the hole of porous copper foil.The active main material of porous copper foil front and back sides has been connected to by the hole of porous copper foil.Cathode expansion inhibits structure, the active main material of foil front and back sides has been connected to by the hole of foil using the linear conductive agent of overlength, it is interspersed in the linear conductive agent of overlength as needlework between the hole of three-dimensional copper foil, fasten the active material on foil two sides, the binding force for reinforcing active main material and foil, can improve pole piece conductivity and peel strength simultaneously.
Description
Technical field
The invention belongs to technical field of lithium ion, the cathode expansion more particularly, to a kind of lithium ion battery inhibits knot
Structure and cathode and preparation method thereof.
Background technique
In today that new energy is changed and sharply developed, new-energy automobile, which has begun, comes into huge numbers of families, and country is also big
Power helps New Energy Industry, faces mileage anxiety, energy density and cycle life to lithium ion battery propose higher want
It asks.According to national ministries and commissions' related guidance file, the year two thousand twenty is arrived, lithium-ion-power cell monomer specific energy is greater than 300Wh/kg, mesh
The preceding graphite cathode system used has been unable to satisfy requirement, this just uses new cathode system -- silicium cathode, but silicon system cathode
Have the shortcomings that one it is obvious, volume expansion is big, therefore, numerous studies be conceived to reduction or inhibit silicon system cathode in use process
In expansion.
Summary of the invention
Inhibit structure and cathode and its preparation side in view of this, expanding the present invention is directed to a kind of cathode of lithium ion battery
Method makes the linear conductive agent of overlength as needlework using with new structural three-dimensional porous copper foil and the linear conductive agent of overlength
It is interspersed between the hole of three-dimensional copper foil, fastens the active material on foil two sides, while improving pole piece conductivity, improve pole
Piece removing alleviates the expansion of cathode main material, reduces cathode pole piece expansion rate, improves integral battery performance.
A kind of cathode expansion inhibition structure of lithium ion battery, including porous copper foil and the linear conductive agent of overlength, it is described
The linear conductive agent of overlength is interspersed between the hole of porous copper foil.Porous copper foil front and back sides have been connected to by the hole of porous copper foil
Active main material.
Cathode expansion inhibits structure mainly linearly to lead by using with new structural three-dimensional porous copper foil and overlength
Electric agent realizes that conventional particles conductive agent structure and conventional linear conductive agent structure can only realize that conducting in a face acts on,
The front and back sides of foil can not be acted on simultaneously, but cathode expansion inhibits structure, the hole for passing through foil using the linear conductive agent of overlength
Hole has been connected to the active main material of foil front and back sides, make the linear conductive agent of overlength be interspersed in as needlework three-dimensional copper foil hole it
Between, fasten the active material on foil two sides, reinforce the binding force of active main material and foil, can improve simultaneously pole piece conductivity and
Peel strength.
In battery charge and discharge process, negative electrode tab is expanded, conventional particles conductive agent structure and conventional linear conductive agent knot
For structure since binding force is weak, anti-swelliong power is poor, and pole piece expansion is big, and active main material is easy to peel off with foil cracking in pole piece, still
Cathode expansion inhibits structure to have strong binding force, and cathode expansion can be effectively reduced, so as to improve the charge-discharge characteristic of battery, mention
Battery cycle life is risen, service time of battery is extended.
Preferably, draw ratio >=10,000 of the linear conductive agent of the overlength；Diameter is 0.5-200nm；Preferably, described super
Long linear conductance agent is single-wall carbon tube, double-walled carbon pipe, multi-wall carbon tube, carbon nano-fiber, graphene band and its with these materials
Based on one or more of modified material；Other conductive agents with draw ratio feature can also be used.
Preferably, in the porous aluminium foil, pore size 0.01-2mm；Spacing between Kong Yukong is 0.5-10mm；
Porous aluminium foil with a thickness of 5-30 μm；The surface density of porous copper foil is 25-125g/m2。
Porous copper foil is the copper foil being distributed with hole, and copper foil ontology is run through in hole, and preparation method includes but is not limited to
Hole is pricked, hole is pressed, is corroded, electrolysis, the method that plating etc. can prepare porous distribution copper foil.
The present invention also provides a kind of cathode of lithium ion battery, including cathode as described above expansion to inhibit structure.
Present invention simultaneously provides a kind of cathode of lithium ion battery, including porous aluminium foil and slurry, the slurry includes
The mass ratio of the linear conductive agent of silicon-carbon, graphite, overlength and stick agent, the silicon-carbon and graphite is (0.5~2): (2~20)；
The linear conductive agent of overlength accounts for the 0.01~1.5% of stock quality；Binder accounts for the 2%~10% of stock quality；The slurry applies
Cloth is on porous copper foil.
Preferably, the binder be CMC (sodium carboxymethylcellulose), SBR (butadiene-styrene rubber), PAA (polyacrylic acid),
One of PAN (polyacrylonitrile), PI (polyisoprene), PAM (polyacrylamide), PMMA (polymethyl methacrylate) or
It is two or more；Draw ratio >=10,000 of the linear conductive agent of overlength；Diameter is 0.5-200nm；Preferably, overlength linear conductance
Agent is single-wall carbon tube, double-walled carbon pipe, multi-wall carbon tube, carbon nano-fiber, graphene band and its changing based on these materials
One or more of property material.
The present invention also provides a kind of method for preparing cathode as described above, includes the following steps, silicon-carbon and graphite are pressed
Certain proportion mixing, is added the linear conductive agent of overlength and binder is homogenized, after the completion of homogenate, sieving coating, and coating when institute
It is porous foil with foil, after baking oven is dried, carries out roll-in, cut and cross cutting obtains cathode；Preferably, the thickness of coating
It is 100~200 μm；The temperature of drying is 90~130 DEG C.
By main material needed for cathode, binder, conductive agent and additive according to a certain percentage be sequentially homogenized, then
It is coated with, in coating process, the movement of slurry can make the linear conductive agent of overlength for including in slurry reach foil by foil hole
Another side, the tow sides of foil are interspersed in as needlework, constitute the three-dimensional conductive with intense beam binding force an of entirety
Network is connected to tow sides.Common linear conductance agent cannot achieve interspersed function since draw ratio is small, need to use ultra-long
This purpose just can be achieved in property conductive agent.After coating drying, solvent volatilization further enhances three-dimensional conductive network pair by roll-in
The binding force of foil and active main material can be very good to play the work for inhibiting expansion and cracking in later period battery use process
With can be obtained after cutting and cross cutting has the negative electrode tab for expanding and inhibiting structure.Again with positive plate, diaphragm, protection shell assembling,
Fluid injection obtains the lithium ion battery for inhibiting structure comprising cathode expansion after chemical conversion and partial volume.
The present invention also provides a kind of lithium ion battery, including cathode as described above, anode, diaphragm, the anode includes
One or more of cobalt acid lithium, LiMn2O4, lithium nickelate, nickle cobalt lithium manganate, LiFePO4；The diaphragm is PP (poly- third
Alkene), one of PE (polyacrylate) and its composite membrane.
Compared with the existing technology, a kind of cathode expansion of lithium ion battery of the present invention inhibit structure and cathode and its
Preparation method has the advantage that
The present invention has been connected to the active main material of foil front and back sides using the linear conductive agent of overlength by the hole of foil, makes to surpass
Long linear conductance agent is interspersed between the hole of three-dimensional copper foil as needlework, fastens the active material on foil two sides, reinforces living
Property main material and foil binding force, while improving pole piece conductivity, improve pole piece removing, alleviate cathode main material expansion, drop
Low cathode pole piece expansion rate improves integral battery performance.
Detailed description of the invention
Fig. 1 is the simple structure schematic diagram of negative pole structure；
Specific embodiment
In addition to being defined, technical term used in following embodiment has universal with those skilled in the art of the invention
The identical meanings of understanding.Test reagent used in following embodiment is unless otherwise specified conventional biochemical reagent；It is described
Experimental method is unless otherwise specified conventional method.
Below with reference to embodiment, the present invention will be described in detail.
Embodiment 1
A kind of cathode of lithium ion battery includes porous aluminium foil and slurry, and the slurry includes silicon-carbon, graphite, ultra-long
Property conductive agent and stick agent, the mass ratio of the silicon-carbon and graphite is 1:15；The linear conductive agent of overlength accounts for stock quality
0.1%；Binder accounts for the 4% of stock quality；The slurry is coated on porous copper foil.
The linear conductive agent of overlength is single-wall carbon tube conductive agent, and carbon pipe diameter is 1-2nm, at least 20 μm long, binder
For the mixture of CMC and SBR, and the mass ratio of the two is 1:3.
In the porous aluminium foil, pore size 0.8mm；Spacing between Kong Yukong is 1mm；Porous aluminium foil with a thickness of
10μm；The surface density of porous copper foil is 50g/m2。
A method of cathode as described above is prepared, is included the following steps, silicon-carbon and graphite are mixed in a certain ratio,
The linear conductive agent of overlength is added and binder is homogenized, after the completion of homogenate, sieving coating, coating thickness is 150 μm, when coating
Foil used is that porous foil is rolled after 110 DEG C of baking ovens are dried, cut and cross cutting obtains cathode.
It is the positive plate of anode, composite membrane diaphragm, protection shell assembling with nickle cobalt lithium manganate by the negative electrode tab of above-mentioned preparation
At non-fluid injection battery core, fluid injection is carried out after baking oven baking 12h to moisture up to standard, electrolyte EC:EMC:DMC=2:3:5 is stood
It after for 24 hours, is melted into, degasification and partial volume, obtains the lithium ion battery for inhibiting structure comprising cathode expansion.
Embodiment 2
A kind of cathode of lithium ion battery includes porous aluminium foil and slurry, and the slurry includes silicon-carbon, graphite, ultra-long
Property conductive agent and stick agent, the mass ratio of the silicon-carbon and graphite is 1:5；The linear conductive agent of overlength accounts for stock quality
0.1%；Binder accounts for the 4% of stock quality；The slurry is coated on porous copper foil.
The linear conductive agent of overlength is graphene band, and diameter 50nm, long at least 0.5mm, binder is PAA class；
Including porous aluminium foil and slurry, the slurry includes silicon-carbon, graphite, the linear conductive agent of overlength and stick agent,
In the porous aluminium foil, pore size 1.5mm；Spacing between Kong Yukong is 2mm；Porous aluminium foil with a thickness of
15μm；The surface density of porous copper foil is 68g/m2。
A method of cathode as described above is prepared, is included the following steps, silicon-carbon and graphite are mixed in a certain ratio,
The linear conductive agent of overlength is added and binder is homogenized, after the completion of homogenate, sieving coating, coating thickness is 150 μm, when coating
Foil used is that porous foil is rolled after 110 DEG C of baking ovens are dried, cut and cross cutting obtains cathode.
It is the positive plate of anode, composite membrane diaphragm, protection shell assembling with nickle cobalt lithium manganate by the negative electrode tab of above-mentioned preparation
At non-fluid injection battery core, fluid injection is carried out after baking oven baking 12h to moisture up to standard, electrolyte EC:EMC:DMC=2:3:5 is stood
It after for 24 hours, is melted into, degasification and partial volume, obtains the lithium ion battery for inhibiting structure comprising cathode expansion.
With non-porous foil when contrast groups are except coating, remaining process is same as Example 1.
Acquired lithium ion battery is subjected to full electricity dismantling, measures the expansion status of negative electrode tab, contrast groups negative electrode tab is compared
Pole piece (control group 1) expansion 45% after rolling, and embodiment 1 includes that cathode expansion inhibits the negative electrode tab of structure compared to stone roller
Pole piece (embodiment 1) expansion only 35% after pressure, reduces the expansion rate of cathode pole piece.
Embodiment 2 includes that cathode expansion inhibits the negative electrode tab of structure only compared to pole piece (embodiment 2) expansion after rolling
Have 32%, reduces the expansion rate of cathode pole piece.
The test result of conductivity: using the conductivity of four probe method test pole piece, contrast groups negative electrode tab conductivity is 5S/
Cm, and what embodiment 1 obtained inhibits the negative electrode tab conductivity of structure for 6S/cm comprising cathode expansion；What embodiment 2 obtained includes
It is 6.5S/cm that cathode expansion, which inhibits the negative electrode tab conductivity of structure,.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Within mind and principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (8)
1. a kind of cathode expansion of lithium ion battery inhibits structure, it is characterised in that: linearly led including porous copper foil and overlength
Electric agent, the linear conductive agent of overlength are interspersed between the hole of porous copper foil；It has been connected to by the hole of porous copper foil porous
The active main material of copper foil front and back sides.
2. the cathode expansion of lithium ion battery according to claim 1 inhibits structure, it is characterised in that: the overlength is linear
The draw ratio of conductive agent >=10,000；Diameter is 0.5-200nm；Preferably, the linear conductive agent of the overlength is single-wall carbon tube, double-walled
Carbon pipe, multi-wall carbon tube, carbon nano-fiber, one of graphene band and its modified material based on these materials or two
Kind or more.
3. the cathode expansion of lithium ion battery according to claim 1 inhibits structure, it is characterised in that: the porous aluminium foil
In, pore size 0.01-2mm；Spacing between Kong Yukong is 0.5-10mm；Porous aluminium foil with a thickness of 5-30 μm；It is porous
The surface density of copper foil is 25-125g/m2。
4. a kind of cathode of lithium ion battery, it is characterised in that: expanded including cathode as claimed in any one of claims 1 to 3
Inhibit structure.
5. a kind of cathode of lithium ion battery, it is characterised in that: including porous aluminium foil and slurry, the slurry include silicon-carbon,
The mass ratio of the linear conductive agent of graphite, overlength and stick agent, the silicon-carbon and graphite is (0.5~2): (2~20)；It is ultra-long
Property conductive agent accounts for the 0.01~1.5% of stock quality；Binder accounts for the 2%~10% of stock quality；The slurry is coated on more
On the copper foil of hole.
6. the cathode of lithium ion battery according to claim 5, it is characterised in that: the binder be CMC, SBR, PAA,
One or more of PAN, PI, PAM, PMMA；Draw ratio >=10,000 of the linear conductive agent of overlength；Diameter is 0.5-
200nm；Preferably, the linear conductive agent of overlength is single-wall carbon tube, double-walled carbon pipe, multi-wall carbon tube, carbon nano-fiber, graphene band
And its one or more of modified material based on these materials.
7. a kind of method for preparing cathode as claimed in claim 5, it is characterised in that: include the following steps, by silicon-carbon and stone
Ink is mixed in a certain ratio, and the linear conductive agent of overlength is added and binder is homogenized, after the completion of homogenate, sieving coating；Coating
Shi Suoyong foil is that porous foil is rolled after baking oven is dried, and is cut and cross cutting obtains cathode；Preferably, coating
With a thickness of 100~200 μm；The temperature of drying is 90~130 DEG C.
8. a kind of lithium ion battery, which is characterized in that including cathode as described in claim 4 or 5, anode, diaphragm, it is described just
Pole includes one or more of cobalt acid lithium, LiMn2O4, lithium nickelate, nickle cobalt lithium manganate, LiFePO4；The diaphragm is
One of PP, PE and its composite membrane.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201811409358.4A CN109390586A (en) | 2018-11-23 | 2018-11-23 | A kind of cathode expansion the inhibition structure and cathode and preparation method thereof of lithium ion battery |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110444746A (en) * | 2019-07-25 | 2019-11-12 | 桑顿新能源科技(长沙)有限公司 | A kind of silicon-carbon cathode slurry, preparation method, cathode pole piece and lithium ion battery |
| CN110649322A (en) * | 2019-09-03 | 2020-01-03 | 河南豫清新能源产业有限公司 | Method for manufacturing high-specific-energy lithium ion battery |
| CN112331831A (en) * | 2020-11-06 | 2021-02-05 | 珠海冠宇电池股份有限公司 | Silicon negative plate, preparation method thereof and lithium ion battery |
| CN112331832A (en) * | 2020-11-06 | 2021-02-05 | 珠海冠宇电池股份有限公司 | Silicon negative plate, preparation method thereof and lithium ion battery |
| CN117239064A (en) * | 2023-11-16 | 2023-12-15 | 瑞浦兰钧能源股份有限公司 | Silicon negative electrode piece and preparation method and application thereof |
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Application publication date: 20190226 |