CN109817985A - A kind of lithium ion battery anode slurry stabilizer and preparation method thereof, application - Google Patents
A kind of lithium ion battery anode slurry stabilizer and preparation method thereof, application Download PDFInfo
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- CN109817985A CN109817985A CN201910225377.XA CN201910225377A CN109817985A CN 109817985 A CN109817985 A CN 109817985A CN 201910225377 A CN201910225377 A CN 201910225377A CN 109817985 A CN109817985 A CN 109817985A
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Abstract
The present invention relates to a kind of lithium ion batteries, and in particular to a kind of lithium ion battery anode slurry stabilizer.Stabilizer includes following components: the polar solvent of polyacrylonitrile and dissolution polyacrylonitrile.Polar solvent is N-Methyl pyrrolidone or/and ethyl alcohol.Lithium ion battery anode slurry, including pressing component: CMC, cathode conductive agent, negative electrode active material, SBR, stabilizer below, preparation method are as follows: CMC and deionized water are stirred evenly into addition cathode conductive agent, stir evenly addition negative electrode active material, it stirs evenly and SBR is added, addition stabilizer is stirred evenly, negative electrode slurry is stirred evenly to obtain.Stabilizer of the present invention is applied in battery cathode slurry, and negative electrode slurry TSI can be obviously reduced, improve the stability of negative electrode slurry, and then slurry can be inhibited to settle, and prevents the bad phenomenons such as slurry coating edge drum side.
Description
Technical field
The present invention relates to a kind of lithium ion batteries, and in particular to a kind of lithium ion battery anode slurry stabilizer.
Background technique
Lithium ion battery is widely used in disappearing due to the advantages that its energy density is high, have extended cycle life, green non-pollution
Take the fields such as electronic product, new-energy automobile.Cathode homogenate is very important one of the production process of lithium ion battery, mesh
Be exactly by negative electrode active material (generally natural graphite, artificial graphite, lithium titanate, silicon carbon material etc.), conductive agent, adhesive
It is dispersed in solvent, obtains the negative electrode slurry of certain solid content and viscosity；Wherein, the stability of negative electrode slurry will be closed directly
It is the quality and yield rate coated to subsequent slurry.
With the raising that lithium ion battery requires energy density, secondary granulation technology is more and more at present is applied to cathode
Active material, but the cathode of secondary granulation is due to its large specific surface area, it is more demanding to technique in production slurry process, hold very much
Rheological characteristic easily occur, perhaps settling occurs in the poor situation of stability or slurry coating edge rouses the bad phenomenons such as side.
In Publication No. CN109273717A, a kind of lithium ion battery silicon substrate cathode modified binder is disclosed, wherein
It include polyacrylonitrile, graphene quantum dot etc., bonding of the used polyacrylonitrile as silicon-based anode in binder formula
Agent, it is therefore intended that improve the bond effect of silica-base material, but do not mentioned for the stability of battery cathode slurry, especially pair
In the stability for the negative electrode active material for improving secondary granulation, do not mention.
Summary of the invention
(1) technical problems to be solved
In order to solve the above problem of the prior art, the present invention, which provides, a kind of can significantly improve lithium ion battery anode slurry
The stabilizer of stability；
Correspondingly, the present invention also provides a kind of lithium ion battery anode slurries with high stability；
Correspondingly, the present invention also provides a kind of lithium ion batteries that can significantly improve lithium ion battery anode slurry stability
The preparation method of negative electrode slurry.
(2) technical solution
In order to achieve the above object, the main technical schemes that the present invention uses include:
A kind of lithium ion battery anode slurry stabilizer comprising following components: polyacrylonitrile and dissolution polyacrylonitrile
Polar solvent.
This programme by polyacrylonitrile and polar solvent after mixing, can as lithium ion battery anode slurry stabilizer
To significantly improve the stability of negative electrode slurry, it is especially applied to artificial graphite or/and day containing secondary granulation secondary granulation
The negative electrode slurry of right graphite, our experiments show that, it can be obviously reduced negative electrode slurry TSI (unstability index), improve cathode slurry
The stability of material, and then slurry can be inhibited to settle, prevent the bad phenomenons such as slurry coating edge drum side.
In the preferred embodiment of lithium ion battery anode slurry stabilizer, the polar solvent be N-Methyl pyrrolidone or/
And ethyl alcohol.
In the present solution, N-Methyl pyrrolidone is colourless transparent oil liquid, micro- smell for having amine.Can with water, alcohol, ether,
Ester, ketone, halogenated hydrocarbons, aromatic hydrocarbons and castor oil dissolve each other, and volatility is low, and thermal stability, chemical stability are good, can wave with vapor
Hair, there is hygroscopicity, light sensitive.This programme polar solvent is N-Methyl pyrrolidone, or is ethyl alcohol, and or is N- methylpyrrole
The combination of alkanone and ethyl alcohol, as stabilizer, is applied in lithium ion battery anode slurry for dissolving polyacrylonitrile, can be bright
The aobvious stabilization for improving polyacrylonitrile in battery cathode slurry.
In the preferred embodiment of lithium ion battery anode slurry stabilizer, the polyacrylonitrile is polar solvent weight
0.1%~50%.In this proportional region, the stabilization played is more preferably.
The present invention also provides a kind of lithium ion battery anode slurry stabilizer preparation method, step includes: by polypropylene
Nitrile powder is added in polar solvent, the solution being dispersed with stirring, as stabilizer.
The present invention also provides a kind of application of lithium ion battery anode slurry stabilizer in negative electrode slurry.
The present invention also provides a kind of lithium ion battery anode slurries comprising following components: CMC, cathode conductive agent, cathode
Stabilizer in active material, SBR and above scheme.
CMC: i.e. sodium carboxymethylcellulose, (also known as: sanlose, carboxymethyl cellulose, CMC,
Carboxymethyl, Cellulose Sodium, Sodium salt of Caboxy Methyl Cellulose), it is grape
The cellulose derivative that the sugared degree of polymerization is 100~2000, white fibrous or particulate powder, it is odorless, it is tasteless, there is hygroscopicity,
Insoluble in organic solvent.
SBR: butadiene-styrene rubber, by butadiene and it is styrene copolymerized be made.It is divided into emulsion polymerization by production method and solution is poly-
It closes, comprehensive performance and chemical stability are preferable.
The aforementioned stabilizer and CMC, cathode conductive agent, negative electrode active material can be prepared surely in this programme
Qualitative stronger lithium ion battery anode slurry.
In the priority scheme of lithium ion battery anode slurry of the present invention, each component is respectively as follows: CMC by weight percentage and is
0.2%~2.0%, cathode conductive agent is 0.5%~5%, negative electrode active material is 90%~98%, SBR be 0.8%~
2.5%, stabilizer is 0.2%~5%.
In the present solution, each component is according in above-mentioned percentage range, after compatibility, the effect of battery cathode slurry is best.
In the priority scheme of lithium ion battery anode slurry of the present invention, the cathode conductive agent be acetylene black, carbon nanotube,
The combination of one or more of graphene.
In the priority scheme of lithium ion battery anode slurry of the present invention, the negative electrode active material is the artificial of secondary granulation
The combination of one or more of graphite, natural graphite, lithium titanate, silicon carbon material；
The present invention also provides a kind of preparation methods of above-mentioned lithium ion battery anode slurry comprising following steps:
S1: CMC and deionized water are stirred evenly into obtain CMC glue；
S2: cathode conductive agent is added in gained CMC glue, stirs evenly to obtain conductive gelatin；
S3: negative electrode active material is added in gained conductive gelatin, stirs evenly to obtain negative electrode active feed liquid；
S4: SBR is added in gained negative electrode active feed liquid, stirs evenly to obtain semi-finished product；
S5: the stabilizer is added in gained semi-finished product, stirs evenly to obtain negative electrode slurry.
The preparation method of lithium ion battery anode slurry of the present invention using substep sequentially add CMC glue, cathode conductive agent,
Negative electrode active material, SBR, CMC are first made CMC glue with water, add cathode conductive agent, it is made first to be dispersed in CMC glue
In liquid, add the artificial plumbago negative pole active material such as the biggish secondary granulation of specific surface area, formed negative electrode active material with
Cathode conductive agent conjugate adds SBR and above-mentioned stabilizer.Negative electrode material specific surface area is bigger, material surface be more difficult to by
Liquid wetting, causes slurry unstable.Stabilizer of the invention can obviously improve between bigger serface negative electrode material and liquid
Wetting effect, improve because soak it is difficult due to the unstable situation of slurry that generates, starched to generate stable not easily settled cathode
Material.
(3) beneficial effect
Compared with prior art, the beneficial effects of the present invention are:
1. it is the artificial of secondary granulation that lithium ion battery anode slurry stabilizer of the invention, which is applied to negative electrode active material,
Graphite, natural graphite, artificial graphite, lithium titanate, silicon-carbon battery cathode slurry in, it is (unstable that negative electrode slurry TSI can be obviously reduced
Overall qualitative index), the stability of negative electrode slurry is improved, and then slurry can be inhibited to settle, prevents slurry coating edge drum side etc. no
Good phenomenon.
2. lithium ion battery anode slurry stabilizer preparation method of the invention is simple, at low cost, market prospects are big.
3. it is simple that stabilizer of the present invention is especially applied to the preparation method in lithium ion battery anode slurry, and uses and divide
CMC glue, cathode conductive agent, the mode of negative electrode active material, SBR and stabilizer is added in step, is successfully generated the strong spy of stability
Be not include secondary granulation artificial graphite negative electrode slurry.
Detailed description of the invention
Fig. 1 is the TSI data variation curve graph of embodiment 3-5 and comparative example 1.
Specific embodiment
In order to preferably explain the present invention, in order to understand, below by specific embodiment, present invention work is retouched in detail
It states.
Embodiment 1: lithium ion battery anode slurry stabilizer comprising following components: polyacrylonitrile and polar solvent, institute
State 0.1%~50% that polyacrylonitrile is polar solvent weight.
Preferably, the polyacrylonitrile is the 0.1% of polar solvent weight；
Preferably, the polyacrylonitrile is the 50% of polar solvent weight；
Preferably, the polyacrylonitrile is the 35% of polar solvent weight；
Preferably, the polyacrylonitrile is the 42% of polar solvent weight；
Wherein, polar solvent is N-Methyl pyrrolidone；
Or polar solvent is ethyl alcohol；
Or polar solvent is the mixture of N-Methyl pyrrolidone and ethyl alcohol.
Wherein, lithium ion battery anode slurry stabilizer the preparation method comprises the following steps: that polyacrylonitrile powder is added to polarity is molten
In agent, the solution being dispersed with stirring, as lithium ion battery anode slurry stabilizer.
Embodiment 2:
Lithium ion battery anode slurry comprising following components in percentage by weight: CMC is 0.2%~2.0%, cathode
Conductive agent is 0.5%~5%, negative electrode active material is 90%~98%, SBR is 0.8%~2.5%, steady made from embodiment 1
Determining agent is 0.2%~5%.Wherein, cathode conductive agent is one or more of acetylene black, carbon nanotube, graphene
Combination.Negative electrode active material is one or both of artificial graphite, natural graphite, lithium titanate and the silicon carbon material of secondary granulation
Above combination.Preferably, negative electrode active material is the combination of the artificial graphite and natural graphite of secondary granulation, ratio 1: 1.
Preferably, it is 0.2%, negative conductive that lithium ion battery anode slurry each component is respectively as follows: CMC by weight percentage
Agent is 0.5%, stabilizer made from negative electrode active material 90%, SBR 0.8%, embodiment 1 is 0.2%.
Preferably, the component of lithium ion battery anode slurry each component by weight percentage: CMC 2.0%, negative conductive
Agent is 5%, stabilizer made from negative electrode active material 98%, SBR 2.5%, embodiment 1 is 5%.
Preferably, the component of lithium ion battery anode slurry each component by weight percentage: CMC 1.0%, negative conductive
Agent is 3%, stabilizer made from negative electrode active material 94%, SBR 2%, embodiment 1 is 3%.
Preferably, it is 1.9%, negative conductive that lithium ion battery anode slurry each component is respectively as follows: CMC by weight percentage
Agent is 3%, stabilizer made from negative electrode active material 91%, SBR 2%, embodiment 1 is 2%.
Preferably, it is 1.6%, negative conductive that lithium ion battery anode slurry each component is respectively as follows: CMC by weight percentage
Agent is 0.7%, stabilizer made from negative electrode active material 97%, SBR 1.8%, embodiment 1 is 0.8%.
Embodiment 3:
The preparation of negative electrode slurry, the specific steps are that:
S1: the polyacrylonitrile powder of 1kg is added in 99kgN- methyl pyrrolidone in first stirring container, is stirred
It mixes to uniform and obtains stabilizer.
S2: 0.16kg CMC and 13.14g deionized water is added in second stirring container and stirs obtained CMC glue；
S3: 0.21kg cathode conductive agent Super P (acetylene black) is added in CMC glue, stirs evenly obtained conducting resinl
Liquid.
S4: 10kg second particle artificial graphite is added in conductive gelatin, stirs evenly obtained negative electrode active feed liquid；
S5: 0.53kg SBR is added in negative electrode active feed liquid, stirs evenly obtained semi-finished product；
S6: stabilizer made in 5.32kg step S1 being added in semi-finished product, stirs evenly, by the way that deionized water is added
Slurry viscosity is adjusted to 1500-4500mPas, negative electrode slurry is made.
Embodiment 4:
The preparation of negative electrode slurry, the specific steps are that:
S1: in first stirring container by the polyacrylonitrile powder of 1kg be added to 49kgN- methyl pyrrolidone and
In the mixed liquor of 50kg ethyl alcohol, it is stirred until homogeneous to obtain stabilizer.
S2: 0.16kg CMC and 13.14g deionized water is added in second stirring container and stirs obtained CMC glue；
S3: 0.21kg cathode conductive agent Super P (acetylene black) is added in CMC glue, stirs evenly obtained conducting resinl
Liquid.
S4: 10kg second particle artificial graphite is added in conductive gelatin, stirs evenly obtained negative electrode active feed liquid；
S5: 0.53kg SBR is added in negative electrode slurry negative electrode active feed liquid, stirs evenly obtained negative electrode slurry semi-finished product；
S6: stabilizer made in 5.32kg step S1 is added in negative electrode slurry semi-finished product, stirs evenly, passes through addition
Slurry viscosity is adjusted to 1500-4500mPas and negative electrode slurry is made by deionized water.
Embodiment 5
The preparation of negative electrode slurry, the specific steps are that:
The polyacrylonitrile powder of 1kg: being added in 99kg N-Methyl pyrrolidone by S1 in first stirring container,
It is stirred until homogeneous to obtain stabilizer.
S2: 0.13kg CMC and 10.41kg deionized water is added in second stirring container and stirs obtained CMC glue；
S3: 0.16kg cathode conductive agent Super P is added in CMC glue, stirs evenly obtained conductive gelatin.
S4: sequentially adding 5kg second particle artificial graphite and 5kg primary particle artificial graphite in conductive gelatin, stirring
Uniformly obtained negative electrode slurry negative electrode active feed liquid；
S5: 0.53kg SBR is added in negative electrode slurry negative electrode active feed liquid, stirs evenly obtained negative electrode slurry semi-finished product；
S6: stabilizer made in 3.16kg step S1 is added in negative electrode slurry semi-finished product, stirs evenly, passes through addition
Slurry viscosity is adjusted to 1500-4500mPas and negative electrode slurry is made by deionized water.
Comparative example 1
S1: CMC the and 13.14g deionized water that 0.16kg is added in stirring container, which stirs, is made CMC glue；
S2: 0.21kg cathode conductive agent Super P is added in CMC glue, stirs evenly obtained conductive gelatin.
S3: 10kg second particle artificial graphite is added in conductive gelatin, stirs evenly obtained negative electrode slurry negative electrode active
Feed liquid；
S4: 0.53kg SBR being added in negative electrode slurry negative electrode active feed liquid, stirs evenly, will by the way that deionized water is added
Slurry viscosity is adjusted to 1500-4500mPas and negative electrode slurry is made.
Experimental data:
Comparative example 1 is detected with negative electrode slurry made from embodiment 3, embodiment 4 and embodiment 5 by TSI index,
Obtain data as shown in Figure 1, it is known that, the stability of negative electrode slurry made from 3-5 of the embodiment of the present invention is apparently higher than comparative example
1, it can obtain, the present invention stabilizer obtained by addition is remarkably improved battery with the compatibility of CMC, cathode conductive agent later
The stability of slurry.
The above is to combine specific embodiment to further explanation of the invention, is not intended to limit of the invention
The scope of the patents, it is all using equivalents made by description of the invention and accompanying drawing content, it is applied directly or indirectly in correlation
Technical field, be included within the scope of the present invention.
Claims (10)
1. a kind of lithium ion battery anode slurry stabilizer, which is characterized in that include the following components: polyacrylonitrile and dissolution are poly-
The polar solvent of acrylonitrile.
2. lithium ion battery anode slurry stabilizer as described in claim 1, it is characterised in that: the polar solvent is N- first
Base pyrrolidones or/and ethyl alcohol.
3. lithium ion battery anode slurry stabilizer as described in claim 1, it is characterised in that: the polyacrylonitrile is polarity
The 0.1%~50% of weight of solvent.
4. lithium ion battery anode slurry stabilizer preparation method as described in any one of claims 1-3, which is characterized in that its
Step includes: that polyacrylonitrile powder is added in polar solvent, the solution being dispersed with stirring, as stabilizer.
5. application of the lithium ion battery anode slurry stabilizer as described in claim 1 in negative electrode slurry.
6. a kind of lithium ion battery anode slurry, which is characterized in that include the following components: CMC, cathode conductive agent, cathode are living
Property substance, SBR and the described in any item stabilizers of claim 1-3.
7. lithium ion battery anode slurry as claimed in claim 6, it is characterised in that: each component is distinguished by weight percentage
Are as follows: CMC is 0.2%~2.0%, cathode conductive agent is 0.5%~5%, negative electrode active material is 90%~98%, SBR is
0.8%~2.5%, stabilizer is 0.2%~5%.
8. lithium ion battery anode slurry as claimed in claim 6, it is characterised in that: the cathode conductive agent be acetylene black,
The combination of one or more of carbon nanotube, graphene.
9. lithium ion battery anode slurry as claimed in claim 6, it is characterised in that: the negative electrode active material is secondary makes
The combination of one or more of artificial graphite, natural graphite, lithium titanate and the silicon carbon material of grain.
10. the preparation method of lithium ion battery anode slurry as claimed in claim 6, it is characterised in that: it includes following step
It is rapid:
S1: CMC and deionized water are stirred evenly into obtain CMC glue；
S2: cathode conductive agent is added in gained CMC glue, stirs evenly to obtain conductive gelatin；
S3: negative electrode active material is added in gained conductive gelatin, stirs evenly to obtain negative electrode active feed liquid；
S4: SBR is added in gained negative electrode active feed liquid, stirs evenly to obtain semi-finished product；
S5: the stabilizer is added in gained semi-finished product, stirs evenly to obtain negative electrode slurry.
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| CN110854367A (en) * | 2019-11-21 | 2020-02-28 | 陕西煤业化工技术研究院有限责任公司 | A kind of silicon carbon anode material slurry and preparation method thereof |
| CN110931734A (en) * | 2019-11-15 | 2020-03-27 | 孚能科技(赣州)股份有限公司 | Negative electrode slurry and preparation method thereof, negative electrode sheet and preparation method thereof, lithium ion battery and application thereof |
| CN111029521A (en) * | 2019-11-21 | 2020-04-17 | 安徽益佳通电池有限公司 | Preparation method of slurry for preventing negative electrode coating from curling of lithium battery |
| CN111180659A (en) * | 2019-12-30 | 2020-05-19 | 江西安驰新能源科技有限公司 | Preparation method of lithium ion battery cathode slurry |
| CN111640945A (en) * | 2020-06-18 | 2020-09-08 | 合肥国轩高科动力能源有限公司 | Lithium ion battery anode slurry and preparation method thereof |
| CN111900391A (en) * | 2020-06-19 | 2020-11-06 | 温州大学新材料与产业技术研究院 | A kind of lithium ion battery negative electrode slurry and preparation method thereof |
| CN112635724A (en) * | 2020-10-30 | 2021-04-09 | 山东精工电子科技有限公司 | Lithium ion battery cathode slurry prepared from high-substitution-degree thickening agent and preparation method of lithium ion battery cathode slurry |
| CN116598422A (en) * | 2023-07-19 | 2023-08-15 | 广汽埃安新能源汽车股份有限公司 | Negative plate, electrode assembly, lithium ion battery and electric equipment |
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| CN111900391B (en) * | 2020-06-19 | 2022-01-11 | 温州大学新材料与产业技术研究院 | Lithium ion battery cathode slurry and preparation method thereof |
| CN112635724A (en) * | 2020-10-30 | 2021-04-09 | 山东精工电子科技有限公司 | Lithium ion battery cathode slurry prepared from high-substitution-degree thickening agent and preparation method of lithium ion battery cathode slurry |
| CN116598422A (en) * | 2023-07-19 | 2023-08-15 | 广汽埃安新能源汽车股份有限公司 | Negative plate, electrode assembly, lithium ion battery and electric equipment |
| CN116598422B (en) * | 2023-07-19 | 2024-01-19 | 广汽埃安新能源汽车股份有限公司 | Negative plate, electrode assembly, lithium ion battery and electric equipment |
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