CN106374083A - Silicon-based negative electrode, preparation method thereof and lithium ion battery - Google Patents
Silicon-based negative electrode, preparation method thereof and lithium ion battery Download PDFInfo
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- CN106374083A CN106374083A CN201610911066.5A CN201610911066A CN106374083A CN 106374083 A CN106374083 A CN 106374083A CN 201610911066 A CN201610911066 A CN 201610911066A CN 106374083 A CN106374083 A CN 106374083A
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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
- H01M4/134—Electrodes based on metals, Si or alloys
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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
- H01M4/139—Processes of manufacture
- H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
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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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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The invention provides a silicon-based negative electrode, a preparation method thereof and a lithium ion battery. The silicon-based negative electrode provided by the invention comprises a current collector, wherein the current collector is provided with two oppositely arranged surfaces; one surface is coated with a first active layer, and the other surface is coated with a second active layer. The silicon-based negative electrode provided by the invention is high in structure stability and good in electrochemical performance, the technological conditions of the preparation method thereof are controllable, and the prepared silicon-based negative electrode is stable in performance. The lithium ion battery provided by the invention contains the silicon-based negative electrode, and the lithium ion battery is stable in cycle performance, long in service life and high in safety performance.
Description
Technical field
The invention belongs to cell art is and in particular to a kind of high gram volume silicon substrate negative electrode and preparation method thereof and lithium
Ion battery.
Background technology
Lithium ion battery is widely used in handss with excellent properties such as its high voltage, high-energy-density and long circulation lifes
Machine and Notebook Battery, electrokinetic cell and energy-storage battery etc..Wherein mobile phone and Notebook Battery are accounted for by lithium ion battery completely
According to other kinds of battery is unable to reach the rigors of these portable intelligent device at all.With lithium ion battery technology
Development, its shared ratio in electrokinetic cell energy-storage battery is also increasing, for current development trend, lithium-ion electric
Pond is in one and develops rapidly the stage, has a extensive future.
With smart mobile phone and the lightening, multifunction of notebook computer and the increasing of screen, existing lithium-ion electric
Pond is equally difficult to meet the consumer electronics product requirement increasingly harsh to battery, to effectively improve lithium in the urgent need to new technique
The specific energy of ion battery.Lithium ion battery generally include the big critical material of negative pole, barrier film, electrolyte, positive pole etc. four and other
Auxiliary material.And in four big critical materials, negative pole and positive pole are its core materials, the gram volume of negative pole and positive electrode and embedding de-
Lithium voltage determines the specific energy of lithium ion battery.The positive electrode that at present lithium ion battery is commonly used have cobalt acid lithium, LiMn2O4, three
Unit and LiFePO4, gram volume is between 100～200mah/g；Conventional negative material is carbons negative material, and gram volume exists
Between 250～360mah/g.
Gram volume due to improving negative material is to improve one of effective way of battery specific energy.Currently used for lithium ion
Cell negative electrode material have graphite-like, silicon substrate, tinbase, nano-carbon material and metal-oxide etc..Wherein, silicon based anode material by
In there is highest quality gram volume and relatively low voltage platform and becoming study hotspot, however, silicon based anode material is embedding de-
Along with serious volumetric expansion during lithium, lead to the powder of detached of electroactive material and the continuous shape of solid electrolyte film
Become, directly result in gram volume rapid decay and efficiency for charge-discharge is low, cycle life is short the problems such as wait so that the silicon substrate of high gram volume
Application on lithium ion battery for the negative material is seriously limited.Although occurring at present adopting silicon based anode material, such as carbon
The composite negative pole material of coated Si is overcoming volumetric expansion defect during embedding de- lithium for the silicon, but effect is limited, still exists
During discharge and recharge, this composite still can occur volumetric expansion, thus still the powder of silicon-carbon active material
Change the formation coming off with solid electrolyte film, still directly result in the problems such as capacity attenuation is fast, cycle life is short.Although in silicon substrate
It is added with binding agent in compound negative electrode, but the binder system adhesion strength of routine is limited, in silicon based anode material circulation
During it may appear that stripping between negative electrode active material, thus losing effective electrical contact, thus leading to battery in discharge and recharge
During there is serious volumetric expansion, capacity attenuation is fast, cycle life is short etc. not enough so that the silicon-based anode material of high gram volume
Application on lithium ion battery for the material is seriously limited.
Content of the invention
It is an object of the invention to overcoming the above-mentioned deficiency of prior art, provide a kind of silicon substrate negative electrode and its preparation side
Method, to solve in existing battery charge and discharge process because silicon-based active material occurs volumetric expansion to lead to silicon based electrode piece to be tied
The technical problem that structure is unstable and electrochemistry is poor.
Another object of the present invention is to provide a kind of silicon-based anode lithium ion battery, with solve existing silicon-based anode lithium from
Sub- battery capacity decay is fast, cyclicity is poor, short life technical problem.
In order to realize foregoing invention purpose, one aspect of the present invention, there is provided a kind of silicon substrate negative electrode.Silicon substrate negative electricity of the present invention
Pole includes collector, and described collector includes two surfaces being oppositely arranged, and a surface is coated with the first active layer, Ling Yibiao
Second active layer is coated with face；Wherein,
Described first active layer includes the component of following weight portion:
Silicon based anode material 94.5-96.0 part
First conductive agent 1.0-1.5 part
Modified sbr binding agent 2.5-3.0 part
Described second active layer includes the component of following weight portion:
A kind of another aspect of the present invention, there is provided preparation method of silicon substrate negative electrode.The preparation side of described silicon substrate negative electrode
Method comprises the steps:
Join according to the compound method of electrode slurry according to the component contained by following first active layer slurry and its component ratio
Make the first active layer slurry, described first active layer slurry includes the component of following weight portion:
Join according to the compound method of electrode slurry according to the component contained by following second active layer slurry and its component ratio
Make the second active layer slurry, described second active layer slurry includes the component of following weight portion:
Described first active layer slurry is coated in and includes wherein the one of two surface negative current collectors being oppositely arranged
On surface, drying is processed, and forms the first active layer；
Described second active layer slurry is coated in another surface of described negative current collector, drying is processed, forms second
Active layer.
A kind of another aspect of the invention, there is provided lithium ion battery, described lithium ion battery contains silicon substrate negative electricity of the present invention
Pole or the silicon substrate negative electrode prepared by preparation method of the present invention.
Compared with prior art, silicon substrate negative electrode of the present invention is using the modified sbr binding agent energy contained by the first active layer
Enough strengthen between silicon based anode material, between the first active layer of silicon based anode material and negative current collector, there is preferable caking property
Can, improve the adhesion strength between the first active layer and negative current collector, and the presence due to modified sbr binding agent, improve
The uniformity of the first active layer, and improve the water retainability to electrolyte for first active layer.Second active layer is using conventional
Non-modified sbr binding agent and modified propylene acid binder are combined so that this compound binding agent not only increases the second active layer
Stability Analysis of Structures, and more stable sei film can be formed during initial charge.Just because of this, this first active layer and second
Active layer serves the synergism of electrochemistry, on the basis of significantly improving silicon substrate negative electrode structure stability and high gram volume,
Can make effectively suppress the full electricity bounce-back of silicon substrate negative electrode of the present invention in charge and discharge process and improve following of silicon-based anode
Ring performance.
Silicon substrate negative electrode preparation method of the present invention is in negative current collector side surface coating modified sbr binding agent as silicon substrate
The binder making of negative material becomes water paste, coats conventional non-modified sbr binding agent and modified third in collector opposite side
Olefin(e) acid binding agent compound binding agent becomes water paste as the binder making of silicon based anode material, by the synergistic of two active layers
Effect, so that the silicon substrate negative electricity of preparation has excellent structural stability, can effectively overcome silicon substrate in charge and discharge process multiple
The powder of detached phenomenon of negative electrode active layer closed the volumetric expansion that active material occurs and lead to occurs, and can be so that in charge and discharge
The full electricity bounce-back of silicon substrate negative electrode of the present invention and the cycle performance improving silicon-based anode can effectively be suppressed in electric process.In addition,
Preparation method process conditions of the present invention are controlled, the silicon substrate negative electrode stable performance of preparation.
Lithium ion battery of the present invention is because containing silicon substrate negative electrode of the present invention, therefore, lithium ion battery of the present invention can make
The high silicon based anode material of gram volume is applied, stable cycle performance, long service life, and security performance is high.
Brief description
Below in conjunction with drawings and Examples, the invention will be further described, in accompanying drawing:
Fig. 1 is the process sequence diagram of embodiment of the present invention silicon substrate negative electrode preparation method.
Specific embodiment
In order that the objects, technical solutions and advantages of the present invention become more apparent, with reference to embodiments, to the present invention
It is further elaborated.It should be appreciated that specific embodiment described herein, only in order to explain the present invention, is not used to
Limit the present invention.
The weight portion of embodiment of the present invention Related Component noted in the disclosure not only may refer to each constituent content,
Part by weight between each component can also be represented, therefore, as long as pressing according to the content of embodiment of the present invention description related component
Scaling or reduce all within embodiment of the present invention description scope of disclosure.Specifically, embodiment of the present invention description
Described in weight can be mass unit known to the chemical fields such as μ g, mg, g, kg.
On the one hand, a kind of structure and the good silicon substrate negative electricity of stable electrochemical property, cyclicity are embodiments provided
Pole.Embodiment of the present invention silicon substrate negative electrode includes collector and applies the negative electrode active layer being located at described collection liquid surface.
Wherein, collector contains relative two surface, and described negative electrode active layer is by the first active layer and the second activity
Layer is constituted, and described first active layer to be coated be on a side surface of described collector, described second active layer applies and is located at institute
State on another side surface of collector.
In one embodiment, described first active layer (dry powder) includes the component of following weight portion:
Silicon based anode material 94.5-96.0 part
First conductive agent 1.0-1.5 part
Modified sbr binding agent (modified styrene butadiene rubber binding agent) 2.5-3.0 part
In a particular embodiment, silicon based anode material selects the silicon based anode material of high gram volume, such as from sub- containing oxidation
The silicon based anode material of silicon, or the silicon based anode material containing pure silicon.Wherein, the Asia in the silicon based anode material of the sub- silicon of oxidation
Silicon weight content is not less than 5%, and the pure silicon weight content in the silicon based anode material containing pure silicon is not less than 3%.As in a tool
In body embodiment, silicon based anode material is the sub- silicon+Delanium of oxidation, is mixed with Delanium by synthetic oxidation Asia silicon
Obtain；Or be carbon-coated nano silicon+Delanium, the silicon-based anode being mixed to get with Delanium by the nano-silicon of carbon coating
Material.From the silicon based anode material of this high gram volume, on the one hand there is high gram volume, on the other hand have relatively small
Cubical expansivity.So can assist in structural stability and the chemical stability that negative electrode active layer improves negative electrode further.
Above-mentioned first conductive agent can with conventional conductive agent, in one embodiment, the first conductive agent is aqueouss cnts,
At least one in sp, Ketjen black.Such conductive agent can be effectively dispersed between silicon based anode material, thus improving first
Electric conductivity in active layer, reduces electrode internal resistance.In addition, those conductive agents have good water dispersible, can be in preparation
Dispersed in slurry.
Above-mentioned modification sbr binding agent be with slurry be dispersed in described silicon based anode material surface, the first conductive agent surface or
Person is filled between those components so that having strong adhesive property between the component such as silicon based anode material, first conductive agent, makes
The first active layer that must be formed is integrated, and has strong structural stability.Enhance the first active layer and afflux body surface simultaneously
Bond strength between face, provides the present embodiment silicon substrate negative electrode overall structural stability can, reduces active layer in discharge and recharge
During there is efflorescence bad phenomenon probability of happening because of volumetric expansion.And the mistake that this modified sbr binding agent is coated with slurry
There is in journey less mobility, thus ensure that the uniformity of the active component of the first active layer and the uniform of thickness, providing
The quality uniformity of the present embodiment silicon substrate negative electrode.This modified sbr binding agent also has preferable water retainability, therefore simultaneously
The full electricity bounce-back of silicon-based anode and the cycle performance improving silicon-based anode can effectively be suppressed in charge and discharge process.Wherein, institute
The full electricity bounce-back stated refers to thickness swelling under full power state for the cathode pole piece, specifically calculates according to equation below:
Full electricity bounce-back=100% × (after partial volume cathode pole piece full electricity thickness-pellet thickness is cut out to cathode pole piece after roller)/right
After roller, cathode pole piece cuts out pellet thickness.
In a particular embodiment, this modified sbr binding agent can be purchased from Japanese jsr with city, and specifically Japanese jsr produces
Its solid content of 104a, this 104a is 45%.This modified sbr is to add hydrophilic radical, this hydrophilic on butadiene-styrene latex side chain
Group can rupture with solvent evaporation in coating process, only retains the linking group between silicon-based anode, thus enhancing
Cohesive force between silicon-based anode, reduces the mobility of sbr, improves the uniformity of the first active layer, and improves first
The water retainability to electrolyte for the active layer.
In addition, if when also containing dispersant or other auxiliary agents in the slurry of above-mentioned first active layer (dry powder) of formation, on
State the first active layer (dry powder) and also contain the adjuvant component that cannot volatilize accordingly, such as the dispersant containing 0.5-1.0 weight portion.
In one embodiment, this dispersant is but not just for sodium carboxymethyl cellulose.
In another embodiment, described second active layer (dry powder) includes the component of following weight portion:
In a particular embodiment, silicon based anode material can be as silicon based anode material in above-mentioned first active layer, its
The silicon based anode material of high gram volume can be selected, such as from the silicon based anode material containing the sub- silicon of oxidation, or the silicon containing pure silicon
Base negative material.Wherein, the sub- silicon weight content in the silicon based anode material of the sub- silicon of oxidation is not less than 5%, containing pure silicon
Pure silicon weight content in silicon based anode material is not less than 3%.As in one embodiment, silicon based anode material is that oxidation is sub-
Silicon+Delanium, is mixed to get with Delanium by synthetic oxidation Asia silicon；Or be carbon-coated nano silicon+Delanium,
The silicon based anode material being mixed to get with Delanium by the nano-silicon of carbon coating.From this silicon based anode material, on the one hand
There is high gram volume, on the other hand there is relatively small cubical expansivity.So can assist in negative electrode active layer to enter
One step improves structural stability and the chemical stability of negative electrode.
Above-mentioned second conductive agent can with conventional conductive agent, in one embodiment, the second conductive agent is aqueouss cnts,
At least one in sp, Ketjen black.Such conductive agent can be effectively dispersed between silicon based anode material, thus improving first
Electric conductivity in active layer, reduces electrode internal resistance.In addition, those conductive agents have good water dispersible, can be in preparation
Dispersed in slurry.
Above-mentioned routine non-modified sbr binding agent and modified propylene acid binder form compound binding agent, not only increase the
The Stability Analysis of Structures of two active layers, and make be formed more stable sei film during initial charge in the second active layer.?
In one embodiment, this conventional non-modified sbr binding agent can be directly commercial, such as selects but is purchased from Gao Bafu not just for city and produces
Conventional non-modified sbr binding agent, such as sd-6516 (solid content 49%).In another embodiment, modified propylene acid binder can
With from the commercial Chengdu mattress ground ld150 (solid content that produces of the happy la133 (solid content 15%) producing or Guangzhou sea ease
15%) etc..It is combined so that this compound binding agent and silicon using this conventional non-modified sbr binding agent and modified propylene acid binder
Sill and conductive agent effect, not only increase the Stability Analysis of Structures of the second active layer, and can be formed during initial charge
More stable sei film.
In addition, so that silicon substrate negative electricity has high gram volume has stable structure simultaneously, being embodied as one
In example, the thickness of described first active layer is 95 μm -105 μm.In another specific embodiment, the thickness of described second active layer
For 95 μm -105 μm.
In a particular embodiment, in above-mentioned each silicon substrate negative electrode embodiment, the collector contained by silicon substrate negative electrode is permissible
It is the negative current collector that lithium ion battery is commonly used, such as Copper Foil etc..
Therefore, in the various embodiments described above, silicon substrate negative electrode using the first active layer containing modified sbr binding agent and contains
The second active layer not only Stability Analysis of Structures of conventional non-modified sbr binding agent and modified propylene acid binder compound binding agent, it is to avoid
The bad phenomenon of the active layer powder of detached being occurred due to volumetric expansion in silicon-based anode charge and discharge process, and two activity
Layer creates electrochemistry synergism, on the basis of significantly improving silicon substrate negative electrode structure stability and high gram volume, can make
The full electricity bounce-back of silicon substrate negative electrode of the present invention and the cycle performance improving silicon-based anode can effectively be suppressed in charge and discharge process.
On the other hand, the embodiment of the present invention additionally provides the preparation side of embodiment of the present invention silicon substrate negative electrode mentioned above
Method.In one embodiment, embodiment of the present invention silicon substrate negative electrode preparation method processing step as shown in figure 1, it include as follows
Step:
Step s01. prepares the first active layer slurry: presses according to the component contained by the first active layer slurry and its component ratio
Compound method according to electrode slurry is configured to the first active layer slurry:
Step s02. prepares the second active layer slurry: presses according to the component contained by the second active layer slurry and its component ratio
Compound method according to electrode slurry is configured to the second active layer slurry；
Step s03. is coated with the first active layer in collection liquid surface side: described first active layer slurry is coated in and has
On wherein one surface of two surface negative current collectors being oppositely arranged, drying is processed, and forms the first active layer；
Step s04. is coated with the second active layer in collection liquid surface opposite side: described second active layer slurry is coated in institute
State another surface of negative current collector, drying is processed, form the second active layer.
Specifically, in above-mentioned steps step s01, as one embodiment of the invention, described first active layer slurry comprises
The component of following weight portion, therefore, this first active layer slurry is water paste:
Wherein, the silicon based anode material contained by the first active layer slurry, the first conductive agent, modified sbr binding agent be all as above
In first active layer in text inventive embodiments silicon substrate negative electrode, contained silicon based anode material, the first conductive agent, modified sbr glue
Knot agent, will not be described here.
In order to improve the dispersion of the first active layer slurry and the stability of dispersion, in above-mentioned first active layer slurry
On the basis of contained component, dispersant can also be contained.In a particular embodiment, this dispersant can be 0.5-1.0 weight
The sodium carboxymethyl cellulose of part.
In addition, on the basis of component contained by above-mentioned first active layer slurry, this first active layer slurry can also contain
There is wetting agent or contain the components such as other auxiliary agents of performance being conducive to improving slurry further, in a particular embodiment, profit
Humectant is selected but not just for n- methyl pyrrolidone (nmp), in addition, its content can be the weight portions such as 3.0-5.0 part, such as 4.0
Weight portion.The presence of this wetting agent, can improve the infiltration of the first conductive agent and aqueous solvent, so that it is more preferable with binding agent
Mixing, realize improve the first active layer slurry coating quality.
In one embodiment, by the addition of water such as deionized water, by the viscosity of the first active layer slurry to 3000-
3500mpa.s (23 ± 2 DEG C), to realize the uniform coating of the first active layer slurry it is ensured that the uniformity of active layer.
In above-mentioned steps step s02, as one embodiment of the invention, described second active layer slurry comprises following weight
The component of part, therefore, this second active layer slurry is water paste:
Wherein, the silicon based anode material contained by the second active layer slurry, the second conductive agent and conventional non-modified sbr binding agent
And modified propylene acid binder all as above in the second active layer in text inventive embodiments silicon substrate negative electrode contained silicon substrate bear
Pole material, the second conductive agent and conventional non-modified sbr binding agent and modified propylene acid binder, will not be described here.
Equally, in order to improve the dispersion of the second active layer slurry and the stability of dispersion, in the above-mentioned second activity
On the basis of component contained by layer slurry, dispersant can also be contained.In a particular embodiment, this dispersant can be 0.5-
The sodium carboxymethyl cellulose of 1.0 weight portions.
In addition, on the basis of component contained by above-mentioned second active layer slurry, this second active layer slurry can also contain
There is wetting agent or contain the components such as other auxiliary agents of performance being conducive to improving slurry further, in a particular embodiment, profit
Humectant is selected but not just for n- methyl pyrrolidone (nmp), in addition, its content can be the weight portions such as 3.0-5.0 part, such as 4.0
Weight portion.The presence of this wetting agent, can improve the infiltration of the second conductive agent and aqueous solvent, so that it is more preferable with binding agent
Mixing, realize improve the second active layer slurry coating quality.
In one embodiment, by the addition of water such as deionized water, by the viscosity of the second active layer slurry to 3000-
3500mpa.s (23 ± 2 DEG C), to realize the uniform coating of the second active layer slurry it is ensured that the uniformity of whole active layer.
In above-mentioned first active layer slurry and the second active layer slurry, the deionized water as slurry solvent can also be
The water of other classes used by electrode production or laboratory, such as distilled water etc., no matter being which kind of water, it is to make in the present embodiment
For solvent, therefore, any other water for substituting the deionized water contained by above-mentioned first active layer slurry are all public in the present invention
Within the scope of opening.
In addition, above-mentioned steps s01 and step s02 do not have sequencing.
In above-mentioned steps s03, the first active layer slurry be coated in negative current collector surface side can but not only according to
Conventional coating processes are coated.
In one embodiment, by the amount of the control described first active layer slurry of coating so that formed described first lives
Property layer thickness be 95 μm -105 μm.By controlling the thickness of its coating, and in step s04, between the secondth active layer, play association
Effect acts on, and gives the high gram volume of embodiment of the present invention silicon substrate negative electricity and excellent structural stability and chemical property.
Negative current collector in this step s03 can be the negative current collector that lithium ion battery is commonly used, such as Copper Foil etc..
In above-mentioned steps s04, the second active layer slurry be coated in negative current collector surface opposite side can but not only by
More solito coating processes are coated.
In one embodiment, by the amount of the control described second active layer slurry of coating so that formed described second lives
Property layer thickness be 95 μm -105 μm.By controlling the thickness of its coating, and in step s03, between the second active layer, play synergistic
Effect, gives the high gram volume of embodiment of the present invention silicon substrate negative electricity and excellent structural stability and chemical property.
It is axiomatic that the preparation method of embodiment of the present invention silicon substrate negative electrode, after above-mentioned steps s04, also includes
Other conventional processing steps of pole piece, the such as processing step such as film-making.Before tableting, will be at step s03 and step s04
Pole piece after reason carries out vacuum drying treatment.As one embodiment of the invention, this step s03 and step s04 dried
Condition is 130-140 DEG C, to remove as slurry solvent etc..After step s03 and the process of step s04, pole piece is carried out at vacuum drying
Reason, the condition of vacuum drying treatment is 100-120 DEG C, and drying at a temperature of being somebody's turn to do should be sufficient, such as 8-10 hour.
Therefore, the present embodiment silicon substrate negative electrode preparation method is in negative current collector side surface coating modified sbr binding agent
Binder making as silicon based anode material becomes water paste, coats conventional non-modified sbr binding agent in collector opposite side
Become water paste with modified propylene acid binder compound binding agent as the binder making of silicon based anode material, by two activity
The synergistic effect of layer, so that the silicon substrate negative electricity of preparation has excellent structural stability, can effectively overcome charge and discharge process
Volumetric expansion that middle silicon substrate composite active material occurs and the powder of detached phenomenon of negative electrode active layer that leads to occurs, and can make
Obtain the full electricity bounce-back that can effectively suppress the present embodiment silicon substrate negative electrode in charge and discharge process and the circulation improving silicon-based anode
Performance.In addition, the present embodiment preparation method process conditions are controlled, the silicon substrate negative electrode stable performance of preparation.
Another aspect, based on embodiment of the present invention silicon substrate negative electrode mentioned above and preparation method thereof, the present invention is implemented
Example additionally provides a kind of lithium ion battery.The structure of this lithium ion battery can be such as lithium ion battery conventional structure, wherein, lithium
The present invention is implemented above for negative electricity contained by ion battery embodiment of the present invention silicon substrate negative electrode extremely mentioned above or employing
The silicon substrate negative electrode of example preparation method preparation.
So, because embodiment of the present invention lithium ion battery contains embodiment of the present invention silicon substrate negative electrode mentioned above,
Thus imparting the excellent chemical property of embodiment of the present invention lithium ion battery, such as give embodiment of the present invention lithium ion battery
There is the full electricity bounce-back that can effectively suppress the present embodiment silicon substrate negative electrode and excellent cycle performance, security performance is high, uses
Life-span length, also has high gram volume.
Multiple above-mentioned silicon substrate negative electrodes and preparation method thereof embodiment is now provided, the present invention is carried out further specifically
Bright.
Embodiment 1
Present embodiments provide a kind of silicon substrate negative electrode and preparation method thereof.The present embodiment silicon substrate negative electrode includes negative pole collection
Fluid is located at the negative electrode active layer of described collection liquid surface with applying, and described negative electrode active layer is by the first active layer and the second active layer
Constitute, and described first active layer applies the side being located at collector, the second active layer applies the opposite side being located at collector, wherein,
First active layer contains modified sbr binding agent, and described second active layer contains conventional sbr binding agent and modified propylene acid binder
Compound binding agent.
The present embodiment silicon substrate negative electrode preparation method is as follows:
Step s11. preparation the first active layer slurry:
By silicon-based anode 95.0 weight portion, cnts (aqueouss) 1.5 weight portion, modified sbr binding agent 3.0 weight portion, cmc
0.5 weight portion, nmp 4.0 weight portion, deionized water 140 weight portion carry out being configured to the first active layer slurry.
Step s12. preparation the second active layer slurry:
By silicon-based anode 95.0 weight portion, cnts (aqueouss) 1.5 weight portion, conventional non-modified sbr binding agent 1.0 weight
Part, modified propylene acid binder 2.5 weight portion, nmp 4.0 weight portion, deionized water 140 weight portion carry out being configured to the first work
Property layer slurry.
Described first active layer slurry is coated on negative current collector one side surface step s13., and drying is processed, shape
Become the first active layer that thickness is 95 μm -105 μm；
Described second active layer slurry is coated on another side surface of negative current collector step s14., and drying is processed,
Form 95 μm -105 μm of the second active layer；
Step s15. prepares silicon substrate negative electrode through follow-up common process after processing.
Comparative example 1
By silicon-based anode 95.0 weight portion, cnts (aqueouss) 1.5 weight portion, conventional non-modified sbr binding agent sbr 3.0 weight
Amount part, cmc 0.5 weight portion, nmp 4.0 weight portion, deionized water 140 weight portion are configured to slurry, and according to embodiment 1
Coating method forms 95 μm -105 μm of active layer in negative current collector face coat, forms silicon substrate negative electrode.
Embodiment 2
Present embodiments provide a kind of silicon substrate negative electrode and preparation method thereof.The present embodiment silicon substrate negative electrode includes negative pole collection
Fluid is located at the negative electrode active layer of described collection liquid surface with applying, and described negative electrode active layer is by the first active layer and the second active layer
Constitute, and described first active layer applies the side being located at collector, the second active layer applies the opposite side being located at collector, wherein,
First active layer contains modified sbr binding agent, and described second active layer contains conventional sbr binding agent and modified propylene acid binder
Compound binding agent.
The present embodiment silicon substrate negative electrode preparation method is as follows:
Step s21. preparation the first active layer slurry:
By silicon-based anode 95.5 weight portion, cnts (aqueouss) 1.0 weight portion, modified sbr binding agent 3.0 weight portion, cmc
0.5 weight portion, nmp 4.0 weight portion, deionized water 140 weight portion carry out being configured to the first active layer slurry.
Step s22. preparation the second active layer slurry:
By silicon-based anode 95.5 weight portion, cnts (aqueouss) 1.0 weight portion, conventional non-modified sbr binding agent 1.0 weight
Part, modified propylene acid binder 2.5 weight portion, nmp 4.0 weight portion, deionized water 140 weight portion carry out being configured to the first work
Property layer slurry.
Described first active layer slurry is coated on negative current collector one side surface step s23., and drying is processed, shape
Become the first active layer that thickness is 95 μm -105 μm；
Described second active layer slurry is coated on another side surface of negative current collector step s24., and drying is processed,
Form 95 μm -105 μm of the second active layer；
Step s25. prepares silicon substrate negative electrode through follow-up common process after processing.
Comparative example 2
By silicon-based anode 95.5 weight portion, cnts (aqueouss) 1.0 weight portion, conventional non-modified sbr binding agent sbr 3.0 weight
Amount part, cmc 0.5 weight portion, nmp 4.0 weight portion, deionized water 140 weight portion are configured to slurry, and according to embodiment 1
Coating method forms 95 μm -105 μm μm of active layer in negative current collector face coat, forms silicon substrate negative electrode.
Embodiment 3
Present embodiments provide a kind of silicon substrate negative electrode and preparation method thereof.The present embodiment silicon substrate negative electrode includes negative pole collection
Fluid is located at the negative electrode active layer of described collection liquid surface with applying, and described negative electrode active layer is by the first active layer and the second active layer
Constitute, and described first active layer applies the side being located at collector, the second active layer applies the opposite side being located at collector, wherein,
First active layer contains modified sbr binding agent, and described second active layer contains conventional sbr binding agent and modified propylene acid binder
Compound binding agent.
The present embodiment silicon substrate negative electrode preparation method is as follows:
Step s31. preparation the first active layer slurry:
By silicon-based anode 95.0 weight portion, cnts (aqueouss) 1.2 weight portion, modified sbr binding agent 2.5 weight portion, cmc
0.8 weight portion, nmp 4.0 weight portion, deionized water 140 weight portion carry out being configured to the first active layer slurry.
Step s32. preparation the second active layer slurry:
By silicon-based anode 95.0 weight portion, cnts (aqueouss) 1.2 weight portion, conventional non-modified sbr binding agent 1.5 weight
Part, modified propylene acid binder 2.3 weight portion, nmp 4.0 weight portion, deionized water 140 weight portion carry out being configured to the first work
Property layer slurry.
Described first active layer slurry is coated on negative current collector one side surface step s33., and drying is processed, shape
Become the first active layer that thickness is 95 μm -105 μm；
Described second active layer slurry is coated on another side surface of negative current collector step s34., and drying is processed,
Form 95 μm -105 μm of the second active layer；
Step s35. prepares silicon substrate negative electrode through follow-up common process after processing.
Comparative example 3
By silicon-based anode 95.0 weight portion, cnts (aqueouss) 1.2 weight portion, conventional non-modified sbr binding agent sbr 3.0 weight
Amount part, cmc 0.8 weight portion, nmp 4.0 weight portion, deionized water 140 weight portion are configured to slurry, and according to embodiment 1
Coating method forms 95 μm -105 μm μm of active layer in negative current collector face coat, forms silicon substrate negative electrode.
Electrochemical property test
By above-described embodiment 1-3 provide silicon substrate negative electrode and comparative example 1-3 provide negative plate respectively with positive pole
The more solito flow process such as piece, electrolyte is assembled into lithium ion battery, and each lithium ion battery is carried out as chemical property in following table
Test, wherein, each lithium ion in addition to negative plate difference, other as other all sames such as positive plate, electrolyte.Test knot
Really as shown in the table:
From above-mentioned data, containing silicon substrate negative electrode provided in an embodiment of the present invention, not only gram volume is high for battery, and
Stable cycle performance, full electricity rebound rate is low, and during low temperature discharge, capability retention is of a relatively high.Thus illustrate the embodiment of the present invention
The first active layer contained by silicon substrate negative electrode and the second active layer have played electrochemistry synergistic effect, effective in electrode work
The powder of detached of negative electrode active layer overcoming the volumetric expansion because silicon based anode material in charge and discharge process occurs and leading to is existing
As occurring, while there is excellent structural stability, also there is excellent stable cycle performance, the property such as low full electricity rebound rate
Energy.By this embodiment of the present invention lithium ion battery long service life, stable cycle performance, and security performance are high, and effectively press down
System full electricity rebound phenomena.
The foregoing is only presently preferred embodiments of the present invention, not in order to limit the present invention, all essences in the present invention
Any modification, equivalent and improvement made within god and principle etc., all should be included within protection scope of the present invention.
Claims (10)
1. a kind of silicon substrate negative electrode, including collector, described collector includes two surfaces being oppositely arranged, and a surface is coated with
There is the first active layer, another surface is coated with the second active layer；Wherein,
Described first active layer includes the component of following weight portion:
Silicon based anode material 94.5-96.0 part
First conductive agent 1.0-1.5 part
Modified sbr binding agent 2.5-3.0 part；
Described second active layer includes the component of following weight portion:
2. silicon substrate negative electrode according to claim 1 it is characterised in that: described modification sbr binding agent is that Japanese jsr produces
104a；And/or
Described modified propylene acid binder is the ld150 that the happy la133 producing in Chengdu mattress ground or Guangzhou sea ease produce.
3. silicon substrate negative electrode according to claim 1 it is characterised in that: the thickness of described first active layer be 95 μm -105
μm；And/or the thickness of described second active layer is 95 μm -105 μm；And/or described first conductive agent or/and the second conductive agent are
At least one in aqueouss cnts, sp, Ketjen black.
4. a kind of preparation method of silicon substrate negative electrode it is characterised in that: comprise the steps:
It is configured to according to the compound method of electrode slurry according to the component contained by following first active layer slurry and its component ratio
First active layer slurry, described first active layer slurry includes the component of following weight portion:
It is configured to according to the compound method of electrode slurry according to the component contained by following second active layer slurry and its component ratio
Second active layer slurry, described second active layer slurry includes the component of following weight portion:
Described first active layer slurry is coated in wherein one surface including two surface negative current collectors being oppositely arranged
On, form the first active layer；
Described second active layer slurry is coated in another surface of described negative current collector, forms the second active layer.
5. silicon substrate negative electrode according to claim 4 it is characterised in that: described modification sbr binding agent is that Japanese jsr produces
104a；And/or
Described modified propylene acid binder is that the mattress ground happy extra large ease of la133 or Guangzhou that produces in Chengdu produces ld150.
6. preparation method according to claim 4 it is characterised in that: described first active layer slurry and/or second activity
The also dispersant containing 0.5-1.0 part in layer slurry.
7. preparation method according to claim 6 it is characterised in that: described dispersant be sodium carboxymethyl cellulose.
8. according to the arbitrary described preparation method of claim 4-7 it is characterised in that: by control coat described first active layer
The amount of slurry is so that the thickness of described first active layer being formed is 95 μm -105 μm；And/or by controlling coating described second
The amount of active layer slurry is so that the thickness of described second active layer being formed is 95 μm -105 μm.
9. according to the arbitrary described preparation method of claim 4-7 it is characterised in that: described first conductive agent or/and second is led
Electric agent is aqueouss cnts, sp, at least one in Ketjen black.
10. a kind of lithium ion battery, including negative electrode it is characterised in that: described negative electricity extremely claim 1-3 is arbitrary described
Silicon substrate negative electrode or prepared by the arbitrary described preparation method of claim 4-9.
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