CN109546085A - It is a kind of to lead carbon silicium cathode pole piece of lithium binder and preparation method thereof using high glue - Google Patents
It is a kind of to lead carbon silicium cathode pole piece of lithium binder and preparation method thereof using high glue Download PDFInfo
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Abstract
The present invention relates to a kind of using the high viscous carbon silicium cathode pole piece and preparation method thereof for leading lithium binder, the component including following parts by weight: 1 ~ 3 part of CMC-Li, modified 0.5 ~ 1 part of SBR, 0.1 ~ 1 part of carbon nanotube, 90 ~ 98 parts of carbon silica solution, 0.5 ~ 5 part and 20 ~ 60 parts of deionized water of viscosity modifier；The silicon-carbon cathode material of the application sufficiently combines the embedding lithium capacity of height of silicon and mechanical performance and electric conductivity that carbon is excellent, the mechanical elasticity of carbon material can buffer the huge volume expansion of silicon, electronic conductivity high simultaneously can also supplement the embedding lithium capacity of height of silicon, so that silicon-carbon composite cathode material specific capacity with higher, discharge capacity is higher for the first time, and cycle efficieny is high, cyclical stability greatly improves.
Description
Technical field
The present invention relates to the technical fields of lithium battery, use the high viscous carbon silicium cathode for leading lithium binder more particularly, to a kind of
Pole piece and preparation method thereof.
Background technique
Negative electrode material is to determine one of the key factor of performance of lithium ion battery.Currently, the lithium ion of commercialization
Cell negative electrode material is graphitic carbon material, and the bulk effect of graphite is small, and cycle performance is excellent, while being also excellent ion conductor
And electronic conductor, but its theoretical specific capacity is lower, as high-energy density and long circulation life are wanted in the fields such as power vehicle
It asks, people further investigate negative electrode material, and discovery silicon is the highest lithium ion battery of specific capacity, in national policy to battery
Energy density requires in the case where being continuously improved, and in order to promote the energy density of battery as far as possible, numerous domestic enterprise has been opened
Begin to increase the research and development and application to silicon based anode material.
But during removal lithium embedded, silicon can generate serious volume change (> 300%), and then lead to material dusting, with
Collector and conductive agent lose electrical contact, and capacity is caused to decay rapidly；The unstable solid electrolyte interface film (SEI of silicon face
Film) also seriously limit its cycle life；During removal lithium embedded, with the expansion and contraction of silicon, the SEI film of silicon face is not
Disconnected deformation, rupture, the silicon face exposed will form new SEI film again, cause SEI film gradually to accumulate and thicken, greatly hinder
Diffusion of the lithium ion to silicon particle reduces the embedding lithium capacity of active material.In addition, the electronic conductivity of silicon is very low, silicium cathode
In lithium ion diffusion it is very slow, so urgently furtheing investigate the expansion rate and cycle efficieny for the first time of silicon substrate cathode of lithium battery.
Summary of the invention
The object of the present invention is to provide a kind of using the high viscous carbon silicium cathode pole piece for leading lithium binder, can improve removal lithium embedded mistake
The expansion of silicon in journey improves the cycle efficieny for the first time of lithium battery.
Foregoing invention purpose one of the invention has the technical scheme that
It is a kind of to glue the carbon silicium cathode pole piece for leading lithium binder using height, the component including following parts by weight: 1 ~ 3 part of CMC-Li, change
Property 0.5 ~ 1 part of SBR, 0.1 ~ 1 part of carbon nanotube, 90 ~ 98 parts of carbon silica solution, 0.5 ~ 5 part of viscosity modifier and deionized water
20 ~ 60 parts.
By using above-mentioned technical proposal, the theoretical lithium storage content of silicon is high, and voltage platform is moderate, at room temperature, each silicon
Atom at most in combination with 3.75 lithium atoms, obtains Li15Si4 alloy phase, and corresponding practical storage lithium specific capacity is up to
3579mAh/g, about the 10 of graphite actual specific capacity times；The voltage platform of silicon is slightly above graphite (about 0.4V), charges in low temperature
Or a possibility that causing surface to analyse lithium when quick charge, is small, security performance is better than graphite, however, in electrochemical lithium storage process
In, the process corresponding material volume variation that silicon atom combination lithium atom obtains alloy phase has reached 300% or more, huge in this way
Bulk effect can cause strong mechanical stress, cause between electrode active material and collector lose contacting, active silicon
Also dusting can occur, so that the rapid decaying of electrode reversible capacity is caused, in addition, the intrinsic conductivity of silicon is very low, only 6.7*
10-4S/cm, carbon nanotube, which is added, can be improved the conductivity of silicon；For full battery, cathode interface is formed when chemical conversion SEI film meeting
The lithium ion from positive deintercalation is consumed, and reduces the capacity of battery, if we can find one again outside positive electrode
Lithium source allows the formation of SEI film to consume the lithium ion of extraneous lithium source, ensures that the lithium ion of positive deintercalation will not waste in this way
In formation process, full battery capacity can be finally improved, the process of above-mentioned offer external world lithium source is exactly prelithiation, existing pre-
Lithiumation means have cathode to shift to an earlier date den process, cathode spraying lithium powder method, three layers of electrode method of cathode, be just rich in lithium material method, but these
Method is at high cost, poor operability, and actual effect is simultaneously bad, and CMCLi has just well solved this problem.CMCLi conduct
Cellulosic binder containing lithium is applied in aqueous positive-pole, other than it can play electrochemistry capacitance, relative to traditional CMCNa
With better viscosity and degree of substitution, under the premise of guaranteeing cohesive force comparable with conventional binders, can reduce binder makes
The 30 ~ 50% of dosage substantially increase the energy density of single battery；Carboxymethyl cellulose lithium (CMC-Li) is a kind of ionic
Cellulose derivative has large volume of anion, applies it in the electrolyte of lithium ion battery, with anion volume
Lesser lithium salts is compared, and CMC-Li has many advantages, such as that the conclusion of negative ions can be reduced, meanwhile, CMC-Li replaces heavy metal electricity
The environmental pollution that solution liquid is generated with reducing heavy metal, having many advantages, such as can Natural Degradation, renewable and excellent electric conductivity；
The SBR latex particle cell of silicon is a kind of core-shell structure, is the cross-linked structure of copolymer molecule chain in shell, and shell is hydrophilic
Polar group and surfactant, the aqueous group in SBR form cohesive force in conjunction with Al foil substrate, are conducive to dispersibility and slurry
Expect stability；Oiliness group forms cohesive force in conjunction with negative electrode material, reaches bond effect；But SBR is easy under high potential
It is oxidized, meanwhile, dispersed bad, the modification SBR favorable dispersibility of the application of the SBR in electrode system, and performance is stablized,
It is also not easy to be oxidized under high potential, and modified SBR is in process, reduces the viscosity of system, prevent film-making
Shi Fasheng roll banding；Carbon nanotube is a kind of carbon material of carbonization structure, itself has excellent electric conductivity, simultaneously because its
Depth is small when removal lithium embedded, stroke is short, and as positive electrode, in high rate charge-discharge, polarization is smaller, and the big of pond can be improved
Rate charge-discharge performance；Carbon silica solution is carbon coating silicon nanostructure, compact structure, with excellent dispersibility and it is good and
The compatibility of other components；Recycle viscosity modifier that the sliminess of negative electrode material system is adjusted, prepared silicon
Carbon negative pole material sufficiently combines the embedding lithium capacity of height of silicon and mechanical performance and electric conductivity that carbon is excellent, the mechanical elastic of carbon material
Performance enough buffers the huge volume expansion of silicon, while high electronic conductivity can also supplement the embedding lithium capacity of height of silicon, so that silicon-carbon
Composite negative pole material specific capacity with higher, discharge capacity is higher for the first time, and cycle efficieny is high, and cyclical stability mentions significantly
It is high.
The present invention is further arranged to, and the preparation process of the CMC-Li uses following steps:
(1) 10 ~ 40 parts of CMC-Na, 30 ~ 100 parts of deionized water, 5 ~ 20 parts of the ethyl alcohol that mass fraction is 80%, quality point are weighed
10 ~ 30 parts of sulfuric acid solution that number is 20%, 10 ~ 30 parts of lithium hydroxide that mass fraction is 12%；
(2) in deionized water by CMC-Na dissolution, ethyl alcohol is added, is sufficiently stirred, while it is molten to be added slowly with stirring sulfuric acid
Liquid continues to stir, and to fully reacting, dries at 35 ~ 40 DEG C to constant weight, obtains CMC-H；
(3) CMC-H is dissolved in 35 ~ 40 DEG C of water bath with thermostatic control, is slowly added to lithium hydroxide, continued to stir and filter, 35 ~
It is dry at a temperature of 40 DEG C, obtain CMC-Li.
By using above-mentioned technical proposal, the acidified processing of CMC-Na is successively obtained into CMC-H, using lithium hydroxide
Processing, obtains CMC-Li, such method conversion ratio is higher, is applicable to industrialization, high production efficiency.
The present invention is further arranged to: the degree of substitution of the carboxymethyl cellulose lithium is 0.7 ~ 1.0.
By using above-mentioned technical proposal, the CMC-Li of degree of substitution range structure in pelletized form, structure is more stable, reduces
The reunion of CMC-Li and other components are conducive to the performance of chemical property.
The present invention is further arranged to: the modified SBR is that SBR is carried out to silicic acid anhydride, forms SBR-SiO2Rubber cement.
By using above-mentioned technical proposal, SiO is utilized2Silicic acid anhydride, favorable dispersibility are carried out to SBR, and performance is steady
It is fixed, it is also not easy to be oxidized under high potential, and since the modified surface SBR is more coarse, and introduce low-surface energy substance preparation
Hydrophobic coating, the SBR of hydrophobically modified formation are added in pole piece system, when can effectively prevent film-making the phenomenon that roll banding.
The present invention is further arranged to, and the preparation method of the carbon silica solution includes the following steps:
(1) weighing: 30 ~ 50 parts of esters of acrylic acid, 100 parts of deionized water, 10 ~ 20 parts of carboxymethyl starch ether, silicon powder 30 ~ 40
Part, 10 ~ 15 parts of nano-graphite；
(2) in deionized water by esters of acrylic acid dissolution, carboxymethyl starch ether is added, colloidal sol is made；
(3) silicon powder into colloidal sol keeps its evenly dispersed by strong stirring and sonic oscillation；
(4) nano-graphite and high-speed stirred are added again, stands form carbon silica solution at room temperature.
By using above-mentioned technical proposal, carboxymethyl starch ether is that a certain amount of carboxyl is introduced in starch molecule, institute
It is bigger compared with the molecular weight of common starch with carboxymethyl starch, and show carboxyl intrinsic property such as hydrophily, complexing etc., it can
Suitable for various industries such as thickener, stabilizer, film forming agent, flocculant, binders；Silicon powder is uniformly admixed in colloidal sol in advance
In, silicon substrate microballoon is made, in silicon substrate microballoon outer cladding nano-graphite, the carbon silicon that nanostructure is formed after high-speed stirred is molten
Glue, the colloidal sol have the dispersibility of height, help to dissolve each other with other components.
The present invention is further arranged to, and the viscosity modifier includes the component of following parts by weight: esters of acrylic acid 30 ~
40 parts, 10 ~ 15 parts of sodium carboxymethylcellulose, 5 ~ 10 parts of carbomer, 5 ~ 10 parts and 1 ~ 5 part of POSS of xanthan gum.
By using above-mentioned technical proposal, using esters of acrylic acid, sodium carboxymethylcellulose, carbomer, xanthan gum, POSS
It is mixed, viscosity modifier is made, which has excellent mobility, higher thermal stability and good electricity
Chemical characteristic.
Foregoing invention purpose two of the invention has the technical scheme that
A kind of preparation method using the high viscous carbon silicium cathode pole piece for leading lithium binder, includes the following steps:
(1) in deionized water by CMC-Li dissolution, it is stirred, obtains mixed slurry a；
(2) carbon nanotube, modified SBR progress mechanical stirring are added into carbon silica solution, obtains mixed slurry b；
(3) mixed slurry a, mixed slurry b are mixed, and viscosity modifier is added, high-speed stirred obtains slurry, slurry
Viscosity is 3000 ~ 4000mpas；
(4) on substrate surface by slurry coating, cathode is formed；
(5) drying and sintering, then it is sliced molding.
By using above-mentioned technical proposal, by blending, stirring, round brush, dry sliced molding, simple process, conveniently, system
Piece is high-efficient.
The present invention is further arranged to: the pH value of slurry is 7 ~ 7.5 in step (3).
By using above-mentioned technical proposal, the pH of slurry is limited as alkalescent, slurry is soft, and film forming is preferable, transparent, light
Pool property is good.
In conclusion advantageous effects of the invention are as follows:
1. the application applies aqueous binders CMC-Li in preparing cathode pole piece, CMC-Li aqueous binders, viscosity is high, adds
Dosage is few；Itself contains Li+, be conducive to the output of Li+, have and mend lithium effect, chemical property is good；
2. use carbon silica solution, replaces traditional silicon carbon material, negative electrode material specific capacity with higher, for the first time discharge capacity
For 1000mAh/g or more, and after 400 circulations, coulombic efficiency does not reduce substantially；
3. the negative electrode material is dehydrated the characteristic for forming ester group using carboxyl and hydroxyl at high temperature, further crosslinking reticulates knot
Structure has good rigidity and caking property, so that the stabilization specific capacity of cathode pole piece increases, first charge discharge efficiency is greater than 90%；
4. using modified SBR favorable dispersibility, and performance is stablized, and is also not easy to be oxidized under high potential, and modified SBR
In process, the viscosity for reducing system prevents that roll banding occurs when film-making；
The spike potential difference of 5.CMC-Li binder, oxidationreduction peak is less than PVDF binder, illustrates to react the obstruction being subject to more
Small, CMC-Li binder is more advantageous to the generation of oxidation-reduction reaction, is conducive to lithium battery and plays chemical property；
6. viscosity modifier had both had viscosity controllability, also there is good conductive and higher thermal stability；
7. the method and process for making cathode is simple, formed product rate is high.
Specific embodiment
Invention is further described in detail with reference to embodiments.
One, the preparation process of CMC-Li uses following steps:
(1) 10 ~ 40 parts of CMC-Na, 30 ~ 100 parts of deionized water, 5 ~ 20 parts of the ethyl alcohol that mass fraction is 80%, quality point are weighed
10 ~ 30 parts of sulfuric acid solution that number is 20%, 10 ~ 30 parts of lithium hydroxide that mass fraction is 12%；
(2) in deionized water by CMC-Na dissolution, ethyl alcohol is added, is sufficiently stirred, while it is molten to be added slowly with stirring sulfuric acid
Liquid continues to stir, and to fully reacting, dries at 35 ~ 40 DEG C to constant weight, obtains CMC-H；
(3) CMC-H is dissolved in 35 ~ 40 DEG C of water bath with thermostatic control, is slowly added to lithium hydroxide, continued to stir and filter, 60 ~
It is dry at a temperature of 80 DEG C, obtain CMC-Li.
Two, the preparation process of viscosity modifier uses following steps:
(1) ingredient: 30 ~ 40 parts of esters of acrylic acid, 10 ~ 15 parts of hydroxyethyl cellulose, 5 ~ 10 parts of carbomer, xanthan gum 5 ~ 10
Part and 1 ~ 5 part of POSS；
(2) esters of acrylic acid is added into reaction vessel, mixing speed 50r/min continuously adds hydroxyethyl cellulose and card
Wave nurse, it is to be mixed uniform；
(3) revolving speed is improved to 150r/min, and xanthan gum and POSS is added, mixture is made.
Three, the preparation process of modified SBR uses following steps:
(1) in parts by weight, the hydroxy silicon oil that 3 ~ 5 drops are instilled into 30 ~ 40 parts of SBR, dilutes SBR, keeps infiltration 30min；
(2) 5 ~ 10 parts of SiO are continuously added2, carrying out high-speed stirred is in thick gel.
Four, the preparation process of carbon silica solution uses following steps:
(1) weighing: 30 ~ 50 parts of esters of acrylic acid, 100 parts of deionized water, 10 ~ 20 parts of carboxymethyl starch ether, silicon powder 30 ~ 40
Part, 10 ~ 15 parts of nano-graphite；
(2) in deionized water by esters of acrylic acid dissolution, carboxymethyl starch ether is added, colloidal sol is made；
(3) silicon powder into colloidal sol keeps its evenly dispersed by strong stirring and sonic oscillation；
(4) nano-graphite and high-speed stirred are added again, stands form silicon-carbon colloidal sol at room temperature.
Embodiment one:
It is a kind of to glue the carbon silicium cathode pole piece for leading lithium binder using height, it prepares with the following method:
(1) ingredient: 1 part of CMC-Li, modified 0.5 part of SBR, 0.1 part of carbon nanotube, 90 parts of carbon silica solution, viscosity modifier
0.5 part and 20 parts of deionized water；
(2) in deionized water by CMC-Li dissolution, it is stirred, obtains mixed slurry a；
(3) carbon nanotube, modified SBR progress mechanical stirring are added into carbon silica solution, obtains mixed slurry b；
(4) mixed slurry a, mixed slurry b are mixed, and viscosity modifier is added, high-speed stirred obtains slurry, slurry
Viscosity is 3000mpas, and the pH value of slurry is 7；
(5) on substrate surface by slurry coating, cathode is formed；
(6) drying and sintering, then it is sliced molding.
Embodiment two:
It is a kind of to glue the carbon silicium cathode pole piece for leading lithium binder using height, it prepares with the following method:
(1) ingredient: 1 part of CMC-Li, modified 0.7 part of SBR, 0.3 part of carbon nanotube, 92 parts of carbon silica solution, viscosity modifier
1 part and 30 parts of deionized water；
(2) in deionized water by CMC-Li dissolution, it is stirred, obtains mixed slurry a；
(3) carbon nanotube, modified SBR progress mechanical stirring are added into carbon silica solution, obtains mixed slurry b；
(4) mixed slurry a, mixed slurry b are mixed, and viscosity modifier is added, high-speed stirred obtains slurry, slurry
Viscosity is 3200mpas, and the pH value of slurry is 7.2；
(5) on substrate surface by slurry coating, cathode is formed；
(6) drying and sintering, then it is sliced molding.
Embodiment three:
It is a kind of to glue the carbon silicium cathode pole piece for leading lithium binder using height, it prepares with the following method:
(1) ingredient: 2 parts of CMC-Li, modified 0.8 part of SBR, 0.5 part of carbon nanotube, 94 parts of carbon silica solution, viscosity modifier
2 parts and 40 parts of deionized water；
(2) in deionized water by CMC-Li dissolution, it is stirred, obtains mixed slurry a；
(3) carbon nanotube, modified SBR progress mechanical stirring are added into carbon silica solution, obtains mixed slurry b；
(4) mixed slurry a, mixed slurry b are mixed, and viscosity modifier is added, high-speed stirred obtains slurry, slurry
Viscosity is 3400mpas, and the pH value of slurry is 7.4；
(5) on substrate surface by slurry coating, cathode is formed；
(6) drying and sintering, then it is sliced molding.
Example IV:
It is a kind of to glue the carbon silicium cathode pole piece for leading lithium binder using height, it prepares with the following method:
(1) ingredient: 2 parts of CMC-Li, modified 0.9 part of SBR, 0.7 part of carbon nanotube, 96 parts of carbon silica solution, viscosity modifier
3 parts and 50 parts of deionized water；
(2) in deionized water by CMC-Li dissolution, it is stirred, obtains mixed slurry a；
(3) carbon nanotube, modified SBR progress mechanical stirring are added into carbon silica solution, obtains mixed slurry b；
(4) mixed slurry a, mixed slurry b are mixed, and viscosity modifier is added, high-speed stirred obtains slurry, slurry
Viscosity is 3600mpas, and the pH value of slurry is 7.5；
(5) on substrate surface by slurry coating, cathode is formed；
(6) drying and sintering, then it is sliced molding.
Embodiment five:
It is a kind of to glue the carbon silicium cathode pole piece for leading lithium binder using height, it prepares with the following method:
(1) ingredient: 3 parts of CMC-Li, modified 1 part of SBR, 1 part of carbon nanotube, 98 parts of carbon silica solution, 4 parts of viscosity modifier
With 60 parts of deionized water；
(2) in deionized water by CMC-Li dissolution, it is stirred, obtains mixed slurry a；
(3) carbon nanotube, modified SBR progress mechanical stirring are added into carbon silica solution, obtains mixed slurry b；
(4) mixed slurry a, mixed slurry b are mixed, and viscosity modifier is added, high-speed stirred obtains slurry, slurry
Viscosity is 4000mpas, and the pH value of slurry is 7.5；
(5) on substrate surface by slurry coating, cathode is formed；
(6) drying and sintering, then it is sliced molding.
Comparative example: with Authorization Notice No. in existing patent for CN102683649B Chinese patent as a comparison case.
The testing result of chemical property is as shown in the table:
| Sample | Discharge capacity (mAh/g) for the first time | Initial coulomb efficiency (%) | Coulombic efficiency (%) after 400 circulations |
| Embodiment one | 1135 | 93 | 92 |
| Embodiment two | 1028 | 93 | 92 |
| Embodiment three | 1117 | 94 | 92 |
| Example IV | 1208 | 95 | 93 |
| Embodiment five | 1196 | 93 | 91 |
| Comparative example | 552~583 | 72~85 | 69~80 |
By upper table it is found that the sample of embodiment one ~ five discharge capacity is higher for the first time, and after 400 cycle charge-discharges, coulomb
Efficiency reduction is small, and the silicon expansion rate in negative electrode material is controlled, so that the electrification of negative electrode material prepared by the application
Have excellent performance, and the circulation conservation rate of discharge capacity is higher for the first time relatively.This is because based particles in the silicon-carbon cathode material
It is evenly distributed in the three-dimensional grid in it, three dimensional network structure inhibits the variation of pole piece thickness, and silicon-based active particle is embedding
Volume still will increase during lithium, but the volume increased ruptures SEI film repeatedly, and consumed Li ion is by CMCLi points
The Li that deviates from subchain is supplemented, and substantially increases the first effect and cycle performance of negative electrode material.
The embodiment of present embodiment is presently preferred embodiments of the present invention, not limits protection of the invention according to this
Range, therefore: the equivalence changes that all structures under this invention, shape, principle are done, should all be covered by protection scope of the present invention it
It is interior.
Claims (8)
1. a kind of use the high viscous carbon silicium cathode pole piece for leading lithium binder, it is characterised in that the component including following parts by weight:
1 ~ 3 part of CMC-Li, modified 0.5 ~ 1 part of SBR, 0.1 ~ 1 part of carbon nanotube, 90 ~ 98 parts of carbon silica solution, viscosity modifier 0.5
~ 5 parts and 20 ~ 60 parts of deionized water.
2. the high viscous carbon silicium cathode pole piece for leading lithium binder of a kind of use according to claim 1, it is characterised in that described
The preparation process of CMC-Li uses following steps:
(1) 10 ~ 40 parts of CMC-Na, 30 ~ 100 parts of deionized water, 5 ~ 20 parts of the ethyl alcohol that mass fraction is 80%, quality point are weighed
10 ~ 30 parts of sulfuric acid solution that number is 20%, 10 ~ 30 parts of lithium hydroxide that mass fraction is 12%；
(2) in deionized water by CMC-Na dissolution, ethyl alcohol is added, is sufficiently stirred, while it is molten to be added slowly with stirring sulfuric acid
Liquid continues to stir, and to fully reacting, dries at 35 ~ 40 DEG C to constant weight, obtains CMC-H；
(3) CMC-H is dissolved in 35 ~ 40 DEG C of water bath with thermostatic control, is slowly added to lithium hydroxide, continued to stir and filter, 60 ~
It is dry at a temperature of 80 DEG C, obtain CMC-Li.
3. the high viscous carbon silicium cathode pole piece for leading lithium binder of a kind of use according to claim 1, it is characterised in that: described
The degree of substitution of carboxymethyl cellulose lithium is 0.7 ~ 1.0.
4. the high viscous carbon silicium cathode pole piece for leading lithium binder of a kind of use according to claim 1, it is characterised in that: described
Modified SBR is that SBR is carried out to silicic acid anhydride, forms SBR-SiO2Rubber cement.
5. the high viscous carbon silicium cathode pole piece for leading lithium binder of a kind of use according to claim 1, it is characterised in that described
The preparation method of carbon silica solution includes the following steps:
(1) weighing: 30 ~ 50 parts of esters of acrylic acid, 100 parts of deionized water, 10 ~ 20 parts of carboxymethyl starch ether, silicon powder 30 ~ 40
Part, 10 ~ 15 parts of nano-graphite；
(2) in deionized water by esters of acrylic acid dissolution, carboxymethyl starch ether is added, colloidal sol is made；
(3) silicon powder into colloidal sol keeps its evenly dispersed by strong stirring and sonic oscillation；
(4) nano-graphite and high-speed stirred are added again, stands form carbon silica solution at room temperature.
6. the high viscous carbon silicium cathode pole piece for leading lithium binder of a kind of use according to claim 1, which is characterized in that described
Viscosity modifier includes the component of following parts by weight: 30 ~ 40 parts of esters of acrylic acid, 10 ~ 15 parts of sodium carboxymethylcellulose, card wave
5 ~ 10 parts of nurse, 5 ~ 10 parts and 1 ~ 5 part of POSS of xanthan gum.
7. a kind of preparation side using the high viscous carbon silicium cathode pole piece for leading lithium binder as described in claim 1 ~ 6 any one
Method, it is characterised in that include the following steps:
(1) in deionized water by CMC-Li dissolution, it is stirred, obtains mixed slurry a；
(2) carbon nanotube, modified SBR progress mechanical stirring are added into carbon silica solution, obtains mixed slurry b；
(3) mixed slurry a, mixed slurry b are mixed, and viscosity modifier is added, high-speed stirred obtains slurry, slurry
Viscosity is 3000 ~ 4000mpas；
(4) on substrate surface by slurry coating, cathode is formed；
(5) drying and sintering, then it is sliced molding.
8. a kind of preparation method using the high viscous carbon silicium cathode pole piece for leading lithium binder according to claim 7, special
Sign is: the pH value of slurry is 7 ~ 7.5 in step (3).
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110797538A (en) * | 2019-11-07 | 2020-02-14 | 惠州亿纬锂能股份有限公司 | Silicon-based negative electrode binder, preparation method thereof and application thereof in lithium ion battery |
| CN112751030A (en) * | 2019-10-31 | 2021-05-04 | 苏州微木智能系统有限公司 | Negative pole piece and lithium ion battery thereof |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102206286A (en) * | 2011-05-16 | 2011-10-05 | 北京理工大学 | Preparation method of lithium carboxymethyl cellulose for lithium battery |
| CN102683649A (en) * | 2011-03-11 | 2012-09-19 | 同济大学 | Method for preparing lithium ion battery carbon silicon anode material |
| CN107959027A (en) * | 2017-11-13 | 2018-04-24 | 合肥国轩高科动力能源有限公司 | Silicon-based negative electrode binder of lithium ion battery and preparation method of negative plate containing binder |
-
2018
- 2018-11-29 CN CN201811446118.1A patent/CN109546085B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102683649A (en) * | 2011-03-11 | 2012-09-19 | 同济大学 | Method for preparing lithium ion battery carbon silicon anode material |
| CN102206286A (en) * | 2011-05-16 | 2011-10-05 | 北京理工大学 | Preparation method of lithium carboxymethyl cellulose for lithium battery |
| CN107959027A (en) * | 2017-11-13 | 2018-04-24 | 合肥国轩高科动力能源有限公司 | Silicon-based negative electrode binder of lithium ion battery and preparation method of negative plate containing binder |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112751030A (en) * | 2019-10-31 | 2021-05-04 | 苏州微木智能系统有限公司 | Negative pole piece and lithium ion battery thereof |
| CN110797538A (en) * | 2019-11-07 | 2020-02-14 | 惠州亿纬锂能股份有限公司 | Silicon-based negative electrode binder, preparation method thereof and application thereof in lithium ion battery |
| CN113013385A (en) * | 2019-12-19 | 2021-06-22 | 山西沃特海默新材料科技股份有限公司 | Coating agent, silicon-carbon material and preparation process |
| CN112968177A (en) * | 2021-03-01 | 2021-06-15 | 广州鹏辉能源科技股份有限公司 | Water-based anode slurry composition, water-based anode slurry, preparation method of water-based anode slurry, anode plate, lithium ion battery and power utilization equipment |
| CN112968177B (en) * | 2021-03-01 | 2022-02-22 | 广州鹏辉能源科技股份有限公司 | Water-based anode slurry composition, water-based anode slurry, preparation method of water-based anode slurry, anode plate, lithium ion battery and power utilization equipment |
| KR20230006381A (en) * | 2021-07-02 | 2023-01-10 | 충칭 리훙 파인 케미컬즈 컴퍼니 리미티드 | High-viscosity lithium carboxymethyl cellulose and preparation method therefor and application thereof |
| CN114678490A (en) * | 2022-03-25 | 2022-06-28 | 湖南蒙达新能源材料有限公司 | Lithium ion battery negative plate and preparation method thereof |
| CN116478305A (en) * | 2023-04-19 | 2023-07-25 | 绿能纤材(重庆)科技有限公司 | Synthetic preparation method of high-purity lithium battery-grade sodium carboxymethyl cellulose |
| CN117239108A (en) * | 2023-09-26 | 2023-12-15 | 绿能纤材(重庆)科技有限公司 | Silicon-carbon negative electrode material containing carboxymethyl cellulose salt, preparation method thereof, negative electrode plate and lithium ion battery |
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Effective date of registration: 20221013 Address after: No. 4, Huiling Village, Pengshan District, Meishan City, Sichuan Province, 620860 (Chengmei Petrochemical Park) Patentee after: Meishan Jingrui Electronic Materials Co.,Ltd. Address before: 215168 No.3, Chenghu East Road, Wuzhong Economic Development Zone, Wuzhong District, Suzhou City, Jiangsu Province Patentee before: RUIHONG LITHIUM BATTERY MATERIAL (SUZHOU) Co.,Ltd. |