CN110247017A - For the binder of lithium ion battery silicon substrate cathode, lithium ion battery silicon substrate cathode and preparation method thereof, lithium ion battery - Google Patents
For the binder of lithium ion battery silicon substrate cathode, lithium ion battery silicon substrate cathode and preparation method thereof, lithium ion battery Download PDFInfo
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- CN110247017A CN110247017A CN201910511989.5A CN201910511989A CN110247017A CN 110247017 A CN110247017 A CN 110247017A CN 201910511989 A CN201910511989 A CN 201910511989A CN 110247017 A CN110247017 A CN 110247017A
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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
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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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
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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
- H01M4/621—Binders
- H01M4/622—Binders being polymers
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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 present invention provides a kind of lithium ion battery silicon substrate negative electrode binders, lithium ion battery silicon substrate cathode and preparation method thereof, lithium ion battery.Binder includes the compound of silane coupling agent or silane coupling agent and water-based binder.Lithium ion battery silicon substrate cathode includes silica-base material, conductive additive, graphite material and binder.The preparation method of silicon-based anode is that will add water into raw material to be made into slurry, and on a current collector, drying obtains for coating.Lithium ion battery includes lithium ion battery silicon substrate cathode.The present invention is since the hydroxyl of silane coupling agent can form certain chemical bond with silicon particle, to guarantee and effectively contacting between silicon particle；Weak chemical bond can also be formed with copper foil current collector, make also have preferable adhesion strength between silicon particle and copper foil, therefore the binder has good caking property and certain flexibility, it can inhibit the volume change of pole piece to a certain extent in cyclic process, and effectively keep the adhesion strength between active material and collector.
Description
Technical field
The present invention relates to technical field of lithium ion, more particularly to the bonding for lithium ion battery silicon substrate cathode
Agent, lithium ion battery silicon substrate cathode and preparation method thereof, lithium ion battery.
Background technique
Increasingly in short supply with global non-renewable energy resources, lithium ion battery is as a kind of clean energy resource by more and more
Concern；The especially fast development of electric car, so that the more more and more urgent battery system for needing higher energy density of people.
Silicon has high specific capacity as the negative electrode material of lithium ion battery, it is considered to be most has the next-generation lithium ion of application potential
Battery cathode candidate material.However, the volume change of Si reaches 300% or more, and violent volume becomes in charge and discharge process
Internal stress caused by changing is easy to cause electrode dusting, peels off, influences cyclical stability.In lithium ion battery, binder is
One of an important factor for influencing electrode structure stability.Therefore it is very necessary to develop a kind of binder that silicium cathode is applicable.
Currently, mainly having Kynoar (PVDF) and butadiene-styrene rubber for the binder of electrode material of lithium battery in the market
(SBR)/sodium carboxymethylcellulose (CMC) etc..It is reconfigured after N-Methyl pyrrolidone (NMP) dissolution need to be added when PVDF use
At slurry, during being fabricated to pole piece, the volatilization of solvent had not only polluted environment but also had endangered the health of staff, and bonded
Power and flexibility are all poor, inhibit the effect of pole piece expansion also very limited, and capacity and the multiplying power property for improving battery are relatively more tired
It is difficult.SBR/CMC aqueous binders have large-scale application on the market, but its cohesive force and the effect for inhibiting pole piece to expand have
Limit, while price is slightly higher.For the characteristic of biggish volume change in silicon materials high-specific surface area and cyclic process, need to glue
Knotting strength is big, mechanical strength and flexible all preferable binder.
Currently, having the dedicated binder of some silicium cathodes.As the patent of Publication No. CN108493452A proposes to use
The aqueous solution of galactomannans and fulvic acid compound is binder, the lithium ion battery anode slurries of the aqueous binders by
Active material, conductive agent and binder composition, each component mass ratio are (50-80): (10-30): (10-20).This is aqueous viscous
Knot agent can be coated on active material and conductive agent surface, form high resiliency space, and the volume adapted in electrode charge and discharge process becomes
Change, improve cycle performance of battery, and the aqueous binders raw material sources are extensive, are a kind of environmentally protective compound binding agent.But
It is that the patent only considers that the cohesive force between silicon particle does not account for the adhesion strength between silicon materials and collector.It is for another example public
The patent that the number of opening is CN107017408A proposes using trigonella bean gum water system answering as binder and its in negative electrode of lithium ion battery
With.The lithium ion battery anode slurry of the binder is made of active material, conductive agent and binder, and each component mass ratio is
(50-90):(5-20):(10-30).Trigonella bean gum and its derivative have good water solubility, elasticity and adhesive property, can have
Effect inhibits silicon volume expansion, and enhancing captures silicon fragmentation capability.Similarly, which only considers that the cohesive force between silicon particle does not have
In view of the adhesion strength between silicon materials and collector.For another example the patent of CN105742640A proposes the polypropylene neutralized with part
Acid is the binder of Silicon Based Anode Materials for Lithium-Ion Batteries.Relate to the preparation method of the binder and as made from the binder
Lithium ion battery silicon cathode material.The Lithium polyacrylate that part neutralizes not only increases the dispersibility of binder, and improves
The mechanical property and processability of binder, are conducive to the chemical property for further increasing material.But the patent only considered
Caking property, binder is rigidly too strong, the durability without considering binder.
Summary of the invention
One purpose of first aspect present invention is to provide for a kind of with good caking property and lithium-ion electric flexible
Pond silicon-based anode binder.
First aspect present invention one is further objective is that will make the silicon-based anode of lithium ion battery in cyclic process
Middle pole piece volume change is controllable, and effectively keeps the adhesion strength between active material and collector.
The purpose of second aspect of the present invention is to provide a kind of lithium ion battery silicon substrate cathode.
The purpose of third aspect present invention is to provide a kind of method for preparing lithium ion battery silicon substrate cathode.
The purpose of fourth aspect present invention is to provide the excellent lithium ion battery of cycle performance.
Particularly, the present invention provides a kind of lithium ion battery silicon substrate negative electrode binders, including silane coupling agent and water system
The compound or silane coupling agent that binder is formed.
Optionally, the silane coupling agent includes vinyltriethoxysilane, vinyltrimethoxysilane, vinyl
Three (beta-methoxy ethyoxyl) any one of silane and mercaptopropyltriethoxysilane.
Optionally, the compound includes vinyltriethoxysilane, vinyltrimethoxysilane, vinyl three
(beta-methoxy ethyoxyl) any one of silane and mercaptopropyltriethoxysilane and butadiene-styrene rubber or sodium carboxymethylcellulose are multiple
Close the compound binding agent formed.
Optionally, the compound includes vinyltriethoxysilane, vinyltrimethoxysilane, vinyl three
(beta-methoxy ethyoxyl) any one of silane and mercaptopropyltriethoxysilane and polyacrylic acid or polyacrylate complex
At compound binding agent.
Particularly, the present invention also provides a kind of lithium ion battery silicon substrate cathode, including silica-base material, conductive additive,
Graphite material and the binder.
Optionally, the mass ratio of the silica-base material, the conductive additive, the graphite material and the binder is
5-80:1-10:15-90:1-15。
Optionally, the silica-base material includes nano silicon material, aoxidizes sub- silicon materials, the mixing of silica and elementary silicon
Material, silicon/carbon composite aoxidize sub- any one of silicon/carbon composite and silicon/oxidation Asia silicon/carbon composite.
Particularly, the present invention also provides the preparation method of the lithium ion battery silicon substrate cathode described in one kind, including it is as follows
Step: will add water in the silica-base material, conductive additive, graphite material and the binder, be made into slurry, will be described
Slurry coats on a current collector, and drying obtains the silicon-based anode.
Optionally, the collector is copper foil.
Particularly, the present invention also provides a kind of lithium ion batteries, including the lithium ion battery silicon substrate cathode.
Lithium ion battery silicon substrate negative electrode binder of the invention, since the hydroxyl of silane coupling agent can form one with silicon particle
Fixed chemical bond, to guarantee and effectively contacting between silicon particle；Weak chemical bond can also be formed with copper foil current collector, make silicon
Also there are preferable adhesion strength, therefore the binder using silane coupling agent as silicon-based anode, the bonding between particle and copper foil
Agent has good caking property and certain flexibility, can inhibit the volume change of pole piece to a certain extent in cyclic process,
And the adhesion strength effectively between holding active material and collector.
Silicon face in silicon-based anode of the invention is generally all handled by carbon coating, for the silicon of carbon coating processing
Grain, silane coupling agent can formed weak chemical bond, therefore, silane coupling agent to by carbon coating processing silicon particle also have
There is preferable adhesion strength.
According to the following detailed description of specific embodiments of the present invention in conjunction with the accompanying drawings, those skilled in the art will be brighter
The above and other objects, advantages and features of the present invention.
Detailed description of the invention
Some specific embodiments of the present invention is described in detail by way of example and not limitation with reference to the accompanying drawings hereinafter.
Identical appended drawing reference denotes same or similar part or part in attached drawing.It should be appreciated by those skilled in the art that these
What attached drawing was not necessarily drawn to scale.In attached drawing:
Fig. 1 is according to embodiments of the present invention one lithium ion battery and the lithium ion battery of comparative example is in room temperature, electric current
Cycle performance figure when 1C.
Specific embodiment
First embodiment of the invention provides a kind of lithium ion battery silicon substrate negative electrode binder, can be silane coupling agent.
Here the molecular structural formula of silane coupling agent are as follows: Y-R-Si (OR) 3.In formula, Y is organic functional base, and SiOR is
Siloxy.
Silane coupling agent can be vinyltriethoxysilane, the vinyltrimethoxysilane, (β-first of vinyl three
Oxygen ethyoxyl) any one of silane and mercaptopropyltriethoxysilane.
Lithium ion battery silicon substrate negative electrode binder, is also possible to the compound of silane coupling agent and water-based binder.This is multiple
Close object can be any one of above-mentioned silane coupling agent be compounded to form with butadiene-styrene rubber or sodium carboxymethylcellulose it is compound
Binder；Be also possible to any one of above-mentioned silane coupling agent be compounded to form with polyacrylic acid or polyacrylate it is compound
Binder.
Lithium ion battery silicon substrate negative electrode binder of the invention, since the hydroxyl of silane coupling agent can form one with silicon particle
Fixed chemical bond, to guarantee and effectively contacting between silicon particle；Weak chemical bond can also be formed with copper foil current collector, make silicon
Also there are preferable adhesion strength, therefore the binder using silane coupling agent as silicon-based anode, the bonding between particle and copper foil
Agent has good caking property and certain flexibility, can inhibit the volume change of pole piece to a certain extent in cyclic process,
And the adhesion strength effectively between holding active material and collector.
Silicon face in silicon-based anode of the invention is generally all handled by carbon coating, for the silicon of carbon coating processing
Grain, silane coupling agent can formed weak chemical bond, therefore, silane coupling agent to by carbon coating processing silicon particle also have
There is preferable adhesion strength.
Second embodiment of the invention provides a kind of lithium ion battery silicon substrate cathode, including silica-base material, conductive additive,
Graphite material and the binder.
Specifically a bit, the mass ratio of silica-base material, conductive additive, graphite material and binder is 5-80:1-10:15-
90:1-15。
Silica-base material includes nano silicon material, aoxidizes sub- silicon materials, the mixing material of silica and elementary silicon, silicon/carbon
Composite material aoxidizes sub- any one of silicon/carbon composite and silicon/oxidation Asia silicon/carbon composite.
Third embodiment of the invention provides the preparation method of lithium ion battery silicon substrate cathode described in one kind, by the silicon
Water is added in sill, conductive additive, graphite material and binder, is made into slurry, on a current collector by slurry coating,
Drying obtains the silicon-based anode.
Wherein, collector is copper foil.
The present invention uses binder of the silane coupling agent as lithium ion battery silicon substrate cathode, which has organic official
Can base and siloxy, can simultaneously and inorganic matter and organic matter form strong or weak chemical bond.Due to the binder with
Bonding action between silicon particle can be formed by hydrolytic process, therefore, in the pulping process of silicon-based anode, silicon
Grain, binder stir together in aqueous solution.In the process, which slowly generates adhesion strength with silicon particle.With this side
Formula does slurry, and the viscosity of slurry is the process gradually increased, is conducive to particle and is uniformly mixed, to improve the matter of slurry
Amount.
Fourth embodiment of the invention provides a kind of lithium ion battery, including the lithium ion battery silicon substrate cathode.
In specific example, the present invention provides embodiment one and comparative examples, as follows respectively.
Embodiment one
It takes water as a solvent, is in mass ratio nano silicon material: conductive additive: graphite material: silane coupling agent by raw material
Binder=40:10:40:10 mixing, is made slurry, slurry is evenly coated on copper foil, well-dried, and pole is obtained after slice
Piece, using metal lithium sheet as to electrode, EC/DEC (volume ratio 1:1) solution of 1mol/L LiPF6 as electrolyte, with
Celgard 2300 is diaphragm, is assembled into CR2016 with the silicon substrate pole piece of preparation and metal lithium sheet in the glove box full of argon gas
Property button cell.At room temperature, constant current cyclic charging and discharging test is carried out with battery test system button type battery, charge and discharge
Voltage range is 0.1-1.2V.
Comparative example
It takes water as a solvent, be in mass ratio nano silicon material: conductive additive: graphite material by raw material: CMC/ SBR is viscous
Agent=40:10:40:10 mixing is tied, slurry is made, slurry is evenly coated on copper foil, it is well-dried, pole is obtained after slice
Piece, using metal lithium sheet as to electrode, EC/DEC (volume ratio 1:1) solution of 1mol/L LiPF6 as electrolyte, with
Celgard 2300 is diaphragm, is assembled into CR2016 with the silicon substrate pole piece of preparation and metal lithium sheet in the glove box full of argon gas
Property button cell.At room temperature, constant current cyclic charging and discharging test is carried out with battery test system button type battery, charge and discharge
Voltage range is 0.1-1.2V.
Fig. 1 is according to embodiments of the present invention one lithium ion battery and the lithium ion battery of comparative example is in room temperature, electric current
Cycle performance figure when 1C.As seen from Figure 1, using silane coupling agent be binder when, nano silica-base material button electricity
The cycle performance in pond obtains the cycle performance of battery when being substantially better than under equal conditions using CMC/SBR as binder.
So far, although those skilled in the art will appreciate that present invention has been shown and described in detail herein multiple shows
Example property embodiment still without departing from the spirit and scope of the present invention, still can according to the present disclosure directly
Determine or deduce out many other variations or modifications consistent with the principles of the invention.Therefore, the scope of the present invention is understood that and recognizes
It is set to and covers all such other variations or modifications.
Claims (10)
1. a kind of binder for lithium ion battery silicon substrate cathode, formed including silane coupling agent with water-based binder compound
Object or silane coupling agent.
2. the binder according to claim 1 for lithium ion battery silicon substrate cathode, wherein the silane coupling agent packet
Include vinyltriethoxysilane, vinyltrimethoxysilane, (beta-methoxy ethyoxyl) silane of vinyl three and mercapto propyl three
Any one of Ethoxysilane.
3. the binder according to claim 1 for lithium ion battery silicon substrate cathode, wherein the compound includes second
Alkenyl triethoxysilane, vinyltrimethoxysilane, (beta-methoxy ethyoxyl) silane of vinyl three and three ethoxy of mercapto propyl
The compound binding agent that any one of base silane is compounded to form with butadiene-styrene rubber or sodium carboxymethylcellulose.
4. the binder according to claim 1 for lithium ion battery silicon substrate cathode, wherein the compound includes second
Alkenyl triethoxysilane, vinyltrimethoxysilane, (beta-methoxy ethyoxyl) silane of vinyl three and three ethoxy of mercapto propyl
The compound binding agent that any one of base silane is compounded to form with polyacrylic acid or polyacrylate.
5. in a kind of lithium ion battery silicon substrate cathode, including silica-base material, conductive additive, graphite material and claim 1-4
Described in any item binders for lithium ion battery silicon substrate cathode.
6. lithium ion battery silicon substrate cathode according to claim 5, wherein the silica-base material, the conductive additive,
The mass ratio of the graphite material and the binder is 5-80:1-10:15-90:1-15.
7. lithium ion battery silicon substrate cathode according to claim 5, wherein the silica-base material include nano silicon material,
Aoxidize mixing material, the silicon/carbon composite of sub- silicon materials, silica and elementary silicon, aoxidize sub- silicon/carbon composite and
Any one of silicon/oxidation Asia silicon/carbon composite.
8. a kind of preparation method of the lithium ion battery silicon substrate cathode as described in any one of claim 5-7, including walk as follows
It is rapid: will to be added in the silica-base material, conductive additive, graphite material and binder of any of claims 1-4
Water is made into slurry, and on a current collector by slurry coating, drying obtains the silicon-based anode.
9. the preparation method of lithium ion battery silicon substrate cathode according to claim 8, wherein the collector is copper foil.
10. a kind of lithium ion battery, including lithium ion battery silicon substrate cathode described in any one of claim 5-7.
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Cited By (10)
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| CN110970622A (en) * | 2019-12-18 | 2020-04-07 | 陕西煤业化工技术研究院有限责任公司 | Water-based binder and preparation method and application thereof |
| CN112289987A (en) * | 2020-09-30 | 2021-01-29 | 合肥国轩高科动力能源有限公司 | Organic-inorganic composite silicon-based negative electrode material and preparation method and application thereof |
| CN112290017A (en) * | 2020-09-14 | 2021-01-29 | 超威电源集团有限公司 | Positive lead paste of lead-acid storage battery, preparation method of positive lead paste and lead-acid storage battery |
| CN112467063A (en) * | 2020-11-10 | 2021-03-09 | 南昌大学 | Preparation method of silicon-based negative electrode plate of lithium ion battery |
| CN112592477A (en) * | 2020-11-25 | 2021-04-02 | 深圳市优宝新材料科技有限公司 | Modified organic silicon polymer, preparation method thereof and lithium secondary battery |
| CN112795016A (en) * | 2021-01-26 | 2021-05-14 | 深圳市优宝新材料科技有限公司 | Modified organic silicon polymer, preparation method thereof and lithium secondary battery |
| CN113851609A (en) * | 2021-08-26 | 2021-12-28 | 蜂巢能源科技有限公司 | Silicon-based negative electrode plate, preparation method thereof and all-solid-state lithium ion battery |
| CN114614010A (en) * | 2022-02-25 | 2022-06-10 | 万华化学(四川)有限公司 | Silicon-containing negative electrode slurry of lithium ion battery and preparation method and application thereof |
| CN116802835A (en) * | 2022-07-11 | 2023-09-22 | 宁德时代新能源科技股份有限公司 | Composite material, preparation method thereof, electrode, secondary battery and electricity utilization device |
| CN117199378A (en) * | 2023-11-06 | 2023-12-08 | 浙江吉利控股集团有限公司 | Silicon-based negative electrode material and lithium ion battery |
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