CN108520958A - Polymer-modified binder, electrode slurry and electrode and lithium ion battery - Google Patents

Polymer-modified binder, electrode slurry and electrode and lithium ion battery Download PDF

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Publication number
CN108520958A
CN108520958A CN201810201404.5A CN201810201404A CN108520958A CN 108520958 A CN108520958 A CN 108520958A CN 201810201404 A CN201810201404 A CN 201810201404A CN 108520958 A CN108520958 A CN 108520958A
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CN
China
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polymer
electrode
binder
modified binder
electrode slurry
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CN201810201404.5A
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Chinese (zh)
Inventor
孟亚斌
钟国兵
王继生
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深圳市优特利电源有限公司
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Priority to CN201810201404.5A priority Critical patent/CN108520958A/en
Publication of CN108520958A publication Critical patent/CN108520958A/en

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    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/62Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621Binders
    • H01M4/622Binders being polymers
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/052Li-accumulators
    • H01M10/0525Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries

Abstract

The invention discloses a kind of polymer-modified binder, the electrode slurry containing the polymer-modified binder and electrode and lithium ion batteries.The polymer-modified binder includes the polymer of polymerization formation being carried out by least one of acrylic monomers and the acrylic monomers derivative monomer, and the carboxy moiety contained by the polymer is existed in the form of metal ion carboxylate groups.Electrode slurry of the present invention contains the polymer-modified binder, and electrode of the present invention and lithium ion battery contain the active layer formed by electrode slurry of the present invention.The polymer-modified binder of the present invention has excellent adhesion strength and high elasticity modulus, solubility in a solvent is high, to improve the dispersing uniformity of electrode slurry ingredient, and the transport of charge carrier can also be promoted after the active layer and electrolyte contacts of electrode slurry formation, therefore, there are stable structure in electrode and lithium ion battery charge and discharge process of the present invention, capacity attenuation is slow, has extended cycle life.

Description

Polymer-modified binder, electrode slurry and electrode and lithium ion battery

Technical field

The invention belongs to battery technology fields, and in particular to a kind of polymer-modified binder, electrode slurry and electrode with And lithium ion battery.

Background technology

Lithium ion battery is widely used in hand with excellent properties such as its high voltage, high-energy density and long circulation lifes Machine and Notebook Battery, power battery and energy-storage battery etc..Wherein mobile phone and Notebook Battery are accounted for by lithium ion battery completely According at all other kinds of battery is unable to reach the rigors of these portable intelligent devices.With lithium ion battery technology Development, shared ratio is also increasing in power battery energy-storage battery, for current development trend, lithium-ion electric Pond is in a rapid development stage, has a extensive future.

With the increasing of smart mobile phone and the lightening of laptop, multifunction and screen, existing lithium-ion electric Pond is equally difficult to meet the consumer electronics product requirement increasingly harsh to battery, and there is an urgent need to new techniques to effectively improve lithium The ratio energy of ion battery.Lithium ion battery generally include the four big critical material such as cathode, diaphragm, electrolyte, anode and other Auxiliary material.And in four big critical materials, cathode and anode are its core materials, the specific capacity of cathode and positive electrode and embedding de- Lithium voltage determines the ratio energy of lithium ion battery.The common positive electrode of lithium ion battery has cobalt acid lithium, LiMn2O4, three at present Member and LiFePO4, specific capacity is between 100~200mAh/g;Common negative material is carbons negative material, and specific capacity exists Between 250~360mAh/g.

Specific capacity due to improving negative material is to improve one of the effective way of battery specific energy.Currently used for lithium ion Cell negative electrode material has graphite-like, silicon substrate, tinbase, nano-carbon material and metal oxide etc..Wherein, silicon based anode material by In becoming research hotspot with highest specific discharge capacity and lower voltage platform, however, silicon based anode material is embedding de- Along with serious volume expansion during lithium, lead to the continuous formation of the powder of detached and solid electrolyte film of active material, It directly results in specific capacity rapid decay and efficiency for charge-discharge is low, the problems such as cycle life is short equal so that the silicon substrate of high gram volume is negative Application of the pole material on lithium ion battery is seriously limited.Although occurring using silicon based anode material at present, such as carbon packet The volume expansion defect for covering the composite negative pole material of silicon to overcome silicon during embedding de- lithium, but effect is limited, is still filling During electric discharge, which can still occur volume expansion, to the dusting of silicon-carbon active material still occur The formation to fall off with solid electrolyte film still directly results in the problems such as capacity attenuation is fast, cycle life is short.Although multiple in silicon substrate It closes and is added with binder, conventional such as SBR binders and LA133 binders in negative electrode, but all cannot effectively solve this A problem so that still will appear dusting during circulating battery, cause to lose effective contact between active material, to lead Send a telegraph pond in charge and discharge process there are serious volume expansion, capacity attenuation is fast, cycle life is short the deficiencies of, performance starts to dislike Change.It has been investigated that it is one of the main reasons that existing binder adhesion strength is low, has lower elasticity modulus.

Invention content

It is an object of the invention to overcome the above-mentioned deficiency of the prior art, a kind of adhesion strength is provided and elasticity modulus is high Polymer-modified binder and preparation method thereof, it is low, with lower elasticity modulus to solve existing binder adhesion strength Technical problem.

Another object of the present invention is to provide a kind of electrode slurry, the electricity containing the active layer formed by the electrode slurry Pole and lithium ion battery, to solve existing lithium ion battery, there are serious volume expansion, capacity attenuations in charge and discharge process Soon, the technical issues of the deficiencies of cycle life is short.

In order to achieve the above-mentioned object of the invention, one aspect of the present invention provides a kind of polymer-modified binder.The modification Polymeric binder includes carrying out polymerization shape by least one of acrylic monomers and the acrylic monomers derivative monomer At polymer, and the carboxy moiety contained by the polymer be in the form of metal ion carboxylate groups exist.

Another aspect of the present invention provides a kind of preparation method of polymer-modified binder.It is described polymer-modified viscous Knot agent preparation method includes the following steps:

At least one of acrylic monomers and the acrylic monomers derivative monomer are subjected to polymerisation formation Polymer;

The polymer and metal ion alkali or metal ion carbonate are subjected to neutralization reaction, neutralize the polymer institute The part carboxyl contained.

Further aspect of the present invention provides a kind of electrode slurry.The electrode slurry includes electrode active material, bonding Agent, conductive agent and solvent, the binder include the polymer-modified binder of the present invention.

Another aspect of the invention provides a kind of electrode.The electrode includes collector and is incorporated on the collector Active layer, the active layer is formed by electrode slurry of the present invention.

Further aspect of the present invention, provides a kind of lithium ion battery, and the lithium ion battery includes electrode of the present invention.

Compared with prior art, the polymer-modified binder of the present invention is by being with metal ion by contained carboxy moiety The form of carboxylate groups exists, in this way, assigning the polymer-modified excellent adhesion strength of binder of the invention and high elasticity Modulus, moreover it is possible to the solubility of the polymer-modified binder of the present invention in a solvent is improved, to improve electrode slurry ingredient Dispersing uniformity, and the transport of charge carrier can also be promoted after the active layer and electrolyte contacts of electrode slurry formation.

The polymer-modified binder preparation method of the present invention can ensure that the carboxy moiety in the polymer to be formed is with gold The form for belonging to ion carboxylate groups exists, to ensure that there is the polymer-modified binder prepared stable height to bond Intensity and high elastic modulus.In addition, the polymer-modified binder preparation method process conditions of the present invention are controllable, the modification of preparation is poly- Object Binder Properties are closed to stablize.

Electrode slurry of the present invention uses the polymer-modified binder of the present invention as electrode slurry binder component, to make The dispersing uniformity for obtaining electrode slurry ingredient of the present invention changes after the electrode slurry is formed source/drain due to described Property the polymeric binder high bond strength and high elastic modulus that have so that active layer structure is stablized, and and electrolyte It can also promote the transport of charge carrier after contact.

Electrode of the present invention and lithium ion battery containing electrode of the present invention are due to the work that is formed containing electrode slurry of the present invention Property layer, to ensure that in electrode and lithium ion battery charge and discharge process of the present invention there are stable structure, capacity attenuation is slow, cycle Long lifespan.

Specific implementation mode

In order to make the purpose , technical scheme and advantage of the present invention be clearer, with reference to embodiments, to the present invention It is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, it is not used to Limit the present invention.

The parts by weight of Related Component noted in the disclosure of the embodiment of the present invention not only may refer to each component content, Weight ratio between each component can also be indicated, therefore, as long as being pressed according to the content of specification related component of the embodiment of the present invention Ratio enlargement reduces within specification of embodiment of the present invention scope of disclosure.Specifically, specification of the embodiment of the present invention Described in weight can be mass unit well known to the chemical fields such as μ g, mg, g, kg.

On the one hand, an embodiment of the present invention provides a kind of polymer-modified binders.The polymer-modified binder packet Include the polymer that polymerization formation is carried out by least one of acrylic monomers and the acrylic monomers derivative monomer.

When the polymer-modified binder contains the polymer that the acrylic monomers derivative is formed, an embodiment In, the acrylic monomers derivative includes 3-butenoic acid, 2 methacrylic acids, 2- penetenoic acids, 2-3 methacrylic acids, 3-3 bis- At least one of methacrylic acid.

Therefore, no matter which kind of the monomer of the polymer-modified binder is, the polymer-modified contained polymer Contain carboxyl on molecular structure.And in the polymer-modified binder, the carboxy moiety contained by the polymer is with gold The form for belonging to ion carboxylate groups exists.In this way, the polymer-modified binder has excellent adhesion strength and high Elasticity modulus, moreover it is possible to improve the solubility of the polymer-modified binder in a solvent.Due to the polymer-modified bonding The solubility of agent is high, to improve the dispersing uniformity of electrode slurry ingredient, and the active layer and electricity that electrode slurry is formed It can also promote the transport of charge carrier after solution liquid contact.

In one embodiment, in the polymer-modified binder, the metal ion carboxylate groups molal quantity It is (0.40-0.90) with the ratio between the metal ion carboxylate groups and the carboxyl total moles:1, can be specifically 0.7: 1.It that is to say, in the polymer, having 40% to 90% in contained carboxyl is deposited in the form of metal ion carboxylate groups .It is described to further increase by optimizing the ratio between the metal ion carboxylate groups and the carboxyl quantity The intensity that polymer-modified binder bonds, promotes its elasticity modulus.

In another embodiment, the metal ion in the metal ion carboxylate groups include the Ith race's metal from At least one of son, the IIth race's metal ion.In a particular embodiment, the metal ion includes in sodium, lithium, potassium, calcium, magnesium At least one.By controlling and optimizing the type of metal ion, to improve what the polymer-modified binder bonded Intensity on the basis of promoting its elasticity modulus, further increases the solubility of the polymer-modified binder in a solvent, and Improve the transport capacity of active layer and the charge carrier after electrolyte contacts containing the polymer-modified binder.

It is described polymer-modified in an embodiment described in the various embodiments described above on the basis of polymer-modified binder The molecular weight of the polymer contained by binder is 300,000-300 ten thousand.By controlling the molecular weight of the polymer in the model It encloses, the caking property of the polymer-modified binder can be effectively improved, and it is lower to assign the polymer-modified binder Swelling.

In addition, the embodiment of the present invention additionally provides a kind of preparation method of polymer-modified binder described above.It is described The preparation method of polymer-modified binder includes the following steps:

S01:At least one of acrylic monomers and the acrylic monomers derivative monomer are subjected to polymerisation shape At polymer;

S02:The polymer and metal ion alkali or metal ion carbonate are subjected to neutralization reaction, neutralize the polymerization Part carboxyl contained by object.

Wherein, at least one of the acrylic monomers in step S01 and the acrylic monomers derivative monomer carry out The polymer that polymerisation is formed can be that the condition for carrying out polymerisation according to existing corresponding monomer is reacted.The propylene Acid monomers derivative it is as described above may include 3-butenoic acid, 2 methacrylic acids, 2- penetenoic acids, 2-3 methacrylic acids, At least one of 3-3 dimethacrylates.Therefore, it polymerize the monomer contained by the polymer of formation can be single third Acrylic monomer can also be the single acrylic monomers derivative, can also be acrylic monomers and acrylic acid list certainly The mixture of syntaxy object arbitrary proportion.Therefore, no matter which kind of the monomer of the polymer-modified binder is, the polymer Contain carboxyl on molecular structure.

In step S02, metal ion alkali or metal ion carbonate are capable of providing metal ion and alkali ion, with institute It states the carboxyl contained by polymer and carries out neutralization reaction, to generate metal ion carboxylate groups.In addition, by the polymerization Control is adjusted in object and the metal ion alkali or metal ion carbonate concentration ratio so that metal ion alkali or metal from Sub- carbonate neutralizes the part carboxyl contained by the polymer, so that the carboxy moiety contained by the polymer is with metal The form of ion carboxylate groups exists.In one embodiment, the polymer and the metal ion alkali or metal ion are controlled Carbonate molar concentration ratio so that the metal ion carboxylate groups molal quantity and the metal ion carboxylate groups It is (0.40-0.90) with the ratio between carboxyl total moles:1, preferably 0.7:1.The reaction dissolvent of neutralization reaction can be made It obtains the metal ion alkali or metal ion carbonate provides the solvent of metal and alkali ion, such as but not just for water.

In addition, polymer-modified binder described above can be dissolved in solvent, solid content can be 1%-40%, molten Agent can be the mixture of water, NMP, low alcohol or low alcohol and water, preferably water.Wherein, low alcohol can be ethyl alcohol, propyl alcohol or butanol Deng.

On the other hand, on the basis of polymer-modified binder described above and preparation method thereof, the embodiment of the present invention Additionally provide a kind of electrode slurry.The electrode slurry may include the component contained by traditional lithium-ion battery electrode slurry, such as Contain the components such as electrode active material, binder, conductive agent and solvent.The content of each component can also be according to conventional content. No matter content of the electrode slurry containing component in how many and each component, contained by binder be that modification described above gathers Close object binder.In this way, the dispersing uniformity of the electrode slurry ingredient, when the electrode slurry is formed source/drain Afterwards, due to high bond strength and high elastic modulus that the polymer-modified binder has, so that active layer structure is steady It is fixed, and with the transport that can also promote charge carrier after electrolyte contacts.

In one embodiment, when the electrode slurry includes active material, binder, conductive agent, the active material, bonding Agent, conductive agent weight ratio be (94-96):(0.5-1.0):(1.0-1.5).Institute above is that is to say by optimizing the binder Content ratio between the polymer-modified binder stated and other components so that each component is evenly dispersed, and improves the electricity The stability of pole slurry system, while ingredient plays the effect of the polymer-modified binder so that the electrode slurry shape After source/drain, active layer structure stability and the charge carrier transport performance with electrolyte contacts are improved.

In a particular embodiment, the active material contained by the electrode slurry can be positive active material, can also be Negative electrode active material.Preferably negative electrode active material.When the active material is positive electrode material, the electrode slurry is anode Slurry, at this point, the positive electrode material can be conventional active substance of lithium ion battery anode;When the active material is cathode When substance, the electrode slurry is negative electrode slurry, at this point, the negative electrode slurry can be conventional negative electrode of lithium ion battery activity Substance such as can be at least one of silicon, Si-C composite material, graphite, hard carbon, carbon microspheres negative electrode active material.

The conductive agent may include at least one of carbon nanotube, Super-p, graphene.

In a further embodiment, the electrode slurry can also contain adjuvant component, such as dispersant, described in raising The stability of electrode slurry dispersion.In one embodiment, the weight ratio of the dispersant and the polymer-modified binder For (0.5-1.0):(0.5-1.0).Specifically, the dispersant can with but not only sodium carboxymethylcellulose (CMC).

The electrode slurry can be prepared as follows:

(1) the polymer-modified binder is dissolved in solvent, prepares glue;Wherein, the solid content of the glue For 1%-40%w/w, a concentration of 1%-40%w/w of the polymer-modified binder that is to say.It waits for described polymer-modified Filtering ageing forms modified binder glue after binder fully dissolves;Be solvent can be water, such as deionized water;

(2) conductive agent, electrode active material and solvent are subjected to mixing treatment, add the glue in step (1) Carry out third time mixing treatment;Viscosity-adjusting agent finally is carried out to mixed slurry with solvent.Wherein, the solvent can be water, such as Deionized water.

When the electrode slurry also contains other auxiliary agents such as dispersant (specific such as sodium carboxymethylcellulose (CMC)), first The dispersant is dissolved in solvent, forms dispersant such as CMC glues after filtering ageing, then to the dispersant such as CMC glues Mixing treatment is carried out under vacuum with conductive agent and solvent;Electrode active material is added afterwards and carries out second of batch mixing with solvent Processing;Then the glue and deionized water being added in step (1) carry out third time mixing treatment;Finally with solvent to mixing Slurry carries out viscosity-adjusting agent.Wherein, the solvent can be water, such as deionized water.

In addition, by the control of the electrode slurry each component and content, preferably the viscosity of the electrode slurry is controlled For 3000Pa.s-4000Pa.s (20 DEG C -30 DEG C).By the control and adjusting to the electrode slurry viscosity, each component is improved The uniformity of dispersion improves the stability of the electrode slurry dispersion, described contained by the electrode slurry to coordinate Polymer-modified binder, improve the electrode slurry formed active layer structure stability and with the charge with electrolyte contacts Carrier transport performance.

In another aspect, on the basis of polymer-modified binder described above and each embodiment of the electrode slurry, this Inventive embodiments additionally provide a kind of electrode.The electrode can be the electrode structure of lithium ion battery routine, such as include afflux Body and the active layer for being incorporated in the collection liquid surface.

In one embodiment, when the electrode is negative plate, the collector contained by the electrode is cathode fluid, contained Active layer is negative electrode active layer, such as the active layer containing silicon-carbon negative material.Wherein, the cathode fluid such as can be copper Foil, tinfoil paper, etc. negative current collectors.The thickness of the negative electrode active layer is 40 μm -80 μm.

In another embodiment, when the electrode can also be positive plate, at this point, the collector contained by the electrode is anode Fluid, contained active layer are positive-active layer, the active layer of the positive electrode such as containing lithium ion battery routine.Wherein, institute It can be aluminium foil, alloy aluminum iron foil plus plate current-collecting body to state positive fluid such as.The thickness of the positive-active layer is 60 μm of -100 μ m。

In addition, electrode described above can according to the conventional method that prepare electrode by electrode slurry described above in collector Upper formation active layer, to prepare the electrode.

At the same time, on the basis of the electrode, the embodiment of the present invention additionally provides a kind of lithium ion battery.The lithium from The structure of sub- battery can be such as lithium ion battery conventional structure, such as contains positive plate and negative plate structure, further includes certainly Necessary other structures component.The wherein described positive plate or negative plate or positive plate and negative plate are electrode described above.

The lithium ion battery due to electrode described above and containing the electrode is due to containing the electrode slurry shape At active layer, to ensure that in the electrode and lithium ion battery charge and discharge process there are stable structure, capacity attenuation is slow, It has extended cycle life.

Multiple above-mentioned negative electrodes and preparation method thereof embodiment is now provided, the present invention will be described in further detail.

1. polymer-modified binder embodiment

Embodiment 11

Present embodiments provide a kind of polymer-modified binder and preparation method thereof.The polymer-modified binder packet Acrylic acid polymer is included, and the carboxy moiety contained by the polymer is existed in the form of metal ion sodium carboxylate groups, And the carboxylic acid sodium accounts for the 70% of carboxylic acid sodium and carboxyl sum.

The preparation method of the polymer-modified binder is as follows:

A certain amount of and certain density polyacrylic acid aqueous solution is taken to stir evenly, known to the polyacrylic acid molecular weight;It takes again A certain amount of and certain density sodium hydrate aqueous solution stirs evenly, and the molal weight of the polyacrylic acid is converted into acrylic acid list The molal weight of body, then mole of acrylic monomers that the polyacrylic acid aqueous solution and sodium hydrate aqueous solution are obtained by conversion Quality and the molal weight of sodium hydroxide ratio are 1:0.7 is sufficiently mixed, and is occurred after uniform stirring needed for neutralization reaction obtains Binder.

Embodiment 12

Present embodiments provide a kind of polymer-modified binder and preparation method thereof.The polymer-modified binder packet Polymethacrylic acid polymer is included, and the carboxy moiety contained by the polymer is deposited in the form of metal ion carboxylic acid potassium group , and the carboxylic acid potassium accounts for the 40% of carboxylic acid potassium and carboxyl sum.

The preparation method of the polymer-modified binder is as follows:

A certain amount of and certain density polymethyl aqueous acid is taken to stir evenly, the polymethylacrylic acid molecular weight is Know;It takes a certain amount of and certain density potassium hydroxide aqueous solution to stir evenly again, the molal weight of the polymethylacrylic acid is changed It is counted as the molal weight of methacrylic acid monomer, then by the polymethyl aqueous acid and potassium hydroxide aqueous solution by converting The molal weight of the methacrylic acid monomer arrived and the molal weight ratio of potassium hydroxide are 1:0.4 is sufficiently mixed, and is uniformly stirred Neutralization reaction occurs after mixing and obtains required binder.

Embodiment 13

Present embodiments provide a kind of polymer-modified binder and preparation method thereof.The polymer-modified binder packet Poly- 3-butenoic acid polymer is included, and the carboxy moiety contained by the polymer is deposited in the form of metal ion magnesium carboxylates group , and the magnesium carboxylates account for the 90% of magnesium carboxylates and carboxyl sum.

The preparation method of the polymer-modified binder is as follows:

A certain amount of and certain density poly- 3-butenoic acid aqueous solution is taken to stir evenly, known to the poly- 3-butenoic acid molecular weight; It takes a certain amount of and certain density magnesium hydroxide aqueous solution to stir evenly again, the molal weight of the poly- 3-butenoic acid is converted into 3- The molal weight of butylene acid monomers, then by the poly- 3-butenoic acid aqueous solution and magnesium hydroxide aqueous solution by the obtained 3- butylene that converts The molal weight of acid monomers and the molal weight ratio of magnesium hydroxide are 1:0.45 is sufficiently mixed, and is neutralized after uniform stirring Required binder is obtained by the reaction.

Embodiment 14

Present embodiments provide a kind of polymer-modified binder and preparation method thereof.The polymer-modified binder packet Acrylic acid polymer is included, and the carboxy moiety contained by the polymer is existed in the form of metal ion carboxylic acid potassium group, And the carboxylic acid potassium accounts for the 90% of carboxylic acid potassium and carboxyl sum.

The preparation method of the polymer-modified binder is as follows:

A certain amount of and certain density polyacrylic acid aqueous solution is taken to stir evenly, known to the polyacrylic acid molecular weight;It takes again A certain amount of and certain density potassium hydroxide aqueous solution stirs evenly, and the molal weight of the polyacrylic acid is converted into acrylic acid list The molal weight of body, then mole of acrylic monomers that the polyacrylic acid aqueous solution and potassium hydroxide aqueous solution are obtained by conversion Quality and the molal weight of potassium hydroxide ratio are 1:0.9 is sufficiently mixed, and is occurred after uniform stirring needed for neutralization reaction obtains Binder.

Embodiment 15

Present embodiments provide a kind of polymer-modified binder and preparation method thereof.The polymer-modified binder packet Polymethacrylic acid polymer is included, and the carboxy moiety contained by the polymer is deposited in the form of metal ion magnesium carboxylates group , and the magnesium carboxylates account for the 40% of magnesium carboxylates and carboxyl sum.

The preparation method of the polymer-modified binder is as follows:

A certain amount of and certain density polymethyl aqueous acid is taken to stir evenly, the polymethylacrylic acid molecular weight is Know;It takes a certain amount of and certain density magnesium hydroxide aqueous solution to stir evenly again, the molal weight of the polymethylacrylic acid is changed It is counted as the molal weight of methacrylic acid monomer, then by the polymethyl aqueous acid and magnesium hydroxide aqueous solution by converting The molal weight of the methacrylic acid monomer arrived and the molal weight ratio of magnesium hydroxide are 1:0.2 is sufficiently mixed, and is uniformly stirred Neutralization reaction occurs after mixing and obtains required binder.

Embodiment 16

Present embodiments provide a kind of polymer-modified binder and preparation method thereof.The polymer-modified binder packet Poly- 3-butenoic acid polymer is included, and the carboxy moiety contained by the polymer is deposited in the form of metal ion sodium carboxylate groups , and the carboxylic acid sodium accounts for the 70% of carboxylic acid sodium and carboxyl sum.

The preparation method of the polymer-modified binder is as follows:

A certain amount of and certain density poly- 3-butenoic acid aqueous solution is taken to stir evenly, known to the poly- 3-butenoic acid molecular weight; It takes a certain amount of and certain density sodium hydrate aqueous solution to stir evenly again, the molal weight of the poly- 3-butenoic acid is converted into 3- The molal weight of butylene acid monomers, then by the poly- 3-butenoic acid aqueous solution and sodium hydrate aqueous solution by the obtained 3- butylene that converts The molal weight of acid monomers and the molal weight ratio of sodium hydroxide are 1:0.7 is sufficiently mixed, and is neutralized after uniform stirring Required binder is obtained by the reaction.

2. electrode slurry embodiment

Embodiment 21

Present embodiments provide a kind of electrode slurry and its preparation method.The electrode slurry includes deionized water, cathode Active material, binder, CMC, conductive agent.Wherein, the negative electrode active material material, binder, CMC, conductive agent are each The parts by weight of component are as follows:

Wherein, the active material is Si-C composite material, and the binder is that the modification that embodiment 11 provides is poly- Object binder is closed, the conductive agent is carbon nanotube.And the viscosity control of 21 electrode slurry of the present embodiment is 3000-4000Pa.s (25℃)

The preparation method of the present embodiment electrode slurry includes the following steps:

(1) binder is dissolved in deionized water, solid content 1%-40%, fully filtering ageing is formed after dissolving Modified binder glue;

(2) CMC is dissolved in deionized water, CMC glues is formed after filtering ageing;

(3) the CMC glues and conductive agent and ionized water are subjected to mixing treatment under vacuum;Again by active matter Matter is added with ionized water and carries out second of mixing treatment;It is eventually adding the modified binder glue and deionized water carries out third Secondary mixing treatment;It is eventually adding deionized water and viscosity-adjusting agent is carried out to it.

Embodiment 22

Present embodiments provide a kind of electrode slurry and its preparation method.The electrode slurry includes deionized water, cathode Active material, binder, CMC, conductive agent.Wherein, the negative electrode active material material, binder, CMC, conductive agent are each The parts by weight of component are as follows:

Wherein, the active material is Si-C composite material, and the binder is that the modification that embodiment 12 provides is poly- Object binder is closed, the conductive agent is carbon nanotube.And the viscosity control of 22 electrode slurry of the present embodiment is 3000-4000Pa.s (25℃)

The preparation method of the present embodiment electrode slurry includes the following steps:

(1) binder is dissolved in deionized water, solid content 1%-40%, fully filtering ageing is formed after dissolving Modified binder glue;

(2) CMC is dissolved in deionized water, CMC glues is formed after filtering ageing;

(3) the CMC glues and conductive agent and ionized water are subjected to mixing treatment under vacuum;Again by active matter Matter is added with ionized water and carries out second of mixing treatment;It is eventually adding the modified binder glue and deionized water carries out third Secondary mixing treatment;It is eventually adding deionized water and viscosity-adjusting agent is carried out to it.

Embodiment 23

Present embodiments provide a kind of electrode slurry and its preparation method.The electrode slurry includes deionized water, cathode Active material, binder, CMC, conductive agent.Wherein, the negative electrode active material material, binder, CMC, conductive agent are each The parts by weight of component are as follows:

Wherein, the active material is Si-C composite material, and the binder is that the modification that embodiment 13 provides is poly- Object binder is closed, the conductive agent is carbon nanotube.And the viscosity control of 23 electrode slurry of the present embodiment is 3000-4000Pa.s (25℃)

The preparation method of the present embodiment electrode slurry includes the following steps:

(1) binder is dissolved in deionized water, solid content 1%-40%, fully filtering ageing is formed after dissolving Modified binder glue;

(2) CMC is dissolved in deionized water, CMC glues is formed after filtering ageing;

(3) the CMC glues and conductive agent and ionized water are subjected to mixing treatment under vacuum;Again by active matter Matter is added with ionized water and carries out second of mixing treatment;It is eventually adding the modified binder glue and deionized water carries out third Secondary mixing treatment;It is eventually adding deionized water and viscosity-adjusting agent is carried out to it.

Embodiment 24

Present embodiments provide a kind of electrode slurry and its preparation method.The electrode slurry includes deionized water, cathode Active material, binder, CMC, conductive agent.Wherein, the negative electrode active material material, binder, CMC, conductive agent are each The parts by weight of component are as follows:

Wherein, the active material is Si-C composite material, and the binder is that the modification that embodiment 14 provides is poly- Object binder is closed, the conductive agent is carbon nanotube.And the viscosity control of 24 electrode slurry of the present embodiment is 3000-4000Pa.s (25℃)

The preparation method of the present embodiment electrode slurry includes the following steps:

(1) binder is dissolved in deionized water, solid content 1%-40%, fully filtering ageing is formed after dissolving Modified binder glue;

(2) CMC is dissolved in deionized water, CMC glues is formed after filtering ageing;

(3) the CMC glues and conductive agent and ionized water are subjected to mixing treatment under vacuum;Again by active matter Matter is added with ionized water and carries out second of mixing treatment;It is eventually adding the modified binder glue and deionized water carries out third Secondary mixing treatment;It is eventually adding deionized water and viscosity-adjusting agent is carried out to it.

Embodiment 25

Present embodiments provide a kind of electrode slurry and its preparation method.The electrode slurry includes deionized water, cathode Active material, binder, CMC, conductive agent.Wherein, the negative electrode active material material, binder, CMC, conductive agent are each The parts by weight of component are as follows:

Wherein, the active material is Si-C composite material, and the binder is that the modification that embodiment 15 provides is poly- Object binder is closed, the conductive agent is carbon nanotube.And the viscosity control of 25 electrode slurry of the present embodiment is 3000-4000Pa.s (25℃)

The preparation method of the present embodiment electrode slurry includes the following steps:

(1) binder is dissolved in deionized water, solid content 1%-40%, fully filtering ageing is formed after dissolving Modified binder glue;

(2) CMC is dissolved in deionized water, CMC glues is formed after filtering ageing;

(3) the CMC glues and conductive agent and ionized water are subjected to mixing treatment under vacuum;Again by active matter Matter is added with ionized water and carries out second of mixing treatment;It is eventually adding the modified binder glue and deionized water carries out third Secondary mixing treatment;It is eventually adding deionized water and viscosity-adjusting agent is carried out to it.

Embodiment 26

Present embodiments provide a kind of electrode slurry and its preparation method.The electrode slurry includes deionized water, cathode Active material, binder, CMC, conductive agent.Wherein, the negative electrode active material material, binder, CMC, conductive agent are each The parts by weight of component are as follows:

Wherein, the active material is Si-C composite material, and the binder is that the modification that embodiment 16 provides is poly- Object binder is closed, the conductive agent is carbon nanotube.And the viscosity control of 26 electrode slurry of the present embodiment is 3000-4000Pa.s (25℃)

The preparation method of the present embodiment electrode slurry includes the following steps:

(1) binder is dissolved in deionized water, solid content 1%-40%, fully filtering ageing is formed after dissolving Modified binder glue;

(2) CMC is dissolved in deionized water, CMC glues is formed after filtering ageing;

(3) the CMC glues and conductive agent and ionized water are subjected to mixing treatment under vacuum;Again by active matter Matter is added with ionized water and carries out second of mixing treatment;It is eventually adding the modified binder glue and deionized water carries out third Secondary mixing treatment;It is eventually adding deionized water and viscosity-adjusting agent is carried out to it.

3. lithium ion battery and negative plate embodiment

Embodiment 31

Present embodiments provide a kind of anode plate for lithium ionic cell and the lithium ion battery containing the negative plate.

Negative plate:Including copper foil current collector and 21 negative electrode slurry of embodiment the cathode on the collector is formed in live Property layer, thickness be 55 μm.

Lithium ion battery:After the present embodiment negative plate and traditional lithium-ion battery positive plate, diaphragm are prepared into core, with Electrolyte is assembled into lithium ion battery.

Embodiment 32

Present embodiments provide a kind of anode plate for lithium ionic cell and the lithium ion battery containing the negative plate.

Negative plate:Including copper foil current collector and 22 negative electrode slurry of embodiment the cathode on the collector is formed in live Property layer, thickness be 55 μm

Lithium ion battery:After the present embodiment negative plate and traditional lithium-ion battery positive plate, diaphragm are prepared into core, with Electrolyte is assembled into lithium ion battery.

Embodiment 33

Present embodiments provide a kind of anode plate for lithium ionic cell and the lithium ion battery containing the negative plate.

Negative plate:Including copper foil current collector and 23 negative electrode slurry of embodiment the cathode on the collector is formed in live Property layer, thickness be 55 μm

Lithium ion battery:After the present embodiment negative plate and traditional lithium-ion battery positive plate, diaphragm are prepared into core, with Electrolyte is assembled into lithium ion battery.

Embodiment 34

Present embodiments provide a kind of anode plate for lithium ionic cell and the lithium ion battery containing the negative plate.

Negative plate:Including copper foil current collector and 24 negative electrode slurry of embodiment the cathode on the collector is formed in live Property layer, thickness be 55 μm.

Lithium ion battery:After the present embodiment negative plate and traditional lithium-ion battery positive plate, diaphragm are prepared into core, with Electrolyte is assembled into lithium ion battery.

Embodiment 35

Present embodiments provide a kind of anode plate for lithium ionic cell and the lithium ion battery containing the negative plate.

Negative plate:Including copper foil current collector and 25 negative electrode slurry of embodiment the cathode on the collector is formed in live Property layer, thickness be 55 μm.

Lithium ion battery:After the present embodiment negative plate and traditional lithium-ion battery positive plate, diaphragm are prepared into core, with Electrolyte is assembled into lithium ion battery.

Embodiment 36

Present embodiments provide a kind of anode plate for lithium ionic cell and the lithium ion battery containing the negative plate.

Negative plate:Including copper foil current collector and 26 negative electrode slurry of embodiment the cathode on the collector is formed in live Property layer, thickness be 55 μm.

Lithium ion battery:After the present embodiment negative plate and traditional lithium-ion battery positive plate, diaphragm are prepared into core, with Electrolyte is assembled into lithium ion battery.

Comparative example 31

Present embodiments provide a kind of anode plate for lithium ionic cell and the lithium ion battery containing the negative plate.

Negative plate:Including copper foil current collector and by following negative electrode slurry:

Negative electrode active material material, SBR binders, CMC, the parts by weight of conductive agent each component are as follows:

Wherein, the active material is Si-C composite material, and the binder is Gao Bafu SBR binders, described Conductive agent is carbon nanotube.And the viscosity control of electrode slurry is 3000-4000Pa.s (25 DEG C)

The preparation method of negative electrode slurry includes the following steps:

(1) the SBR binders are dissolved in deionized water, solid content 1%-40%, fully filter ageing after dissolving Form adhesive gelatin;

(2) CMC is dissolved in deionized water, CMC glues is formed after filtering ageing;

(3) the CMC glues and conductive agent and ionized water are subjected to mixing treatment under vacuum;Again by active matter Matter is added with ionized water and carries out second of mixing treatment;It is eventually adding the modified binder glue and deionized water carries out third Secondary mixing treatment;It is eventually adding deionized water and viscosity-adjusting agent is carried out to it.

The negative electrode slurry is coated on the collector and forms negative electrode active layer, thickness is 55 μm

Lithium ion battery:After the present embodiment negative plate and traditional lithium-ion battery positive plate, diaphragm are prepared into core, with Electrolyte is assembled into lithium ion battery.

4 electrochemical property tests

The lithium ion battery that above-described embodiment 31-36 lithium ion batteries provided and comparative example are provided carries out as follows respectively Performance test in table 1, wherein each lithium ion is other than negative plate difference, other are equal for other such as positive plates, electrolyte It is identical.Wherein, test result is as follows shown in table 1 for embodiment 31-36 and comparative example.

From the data in table 1, it can be seen that lithium ion battery of the embodiment of the present invention recycles 300 weeks compared to comparative example lithium ion battery 1C Capacity retention ratio will be higher by 13% afterwards, and the thickness change of battery core also reduces 4.5% after cycle, the full electric thickness swelling of negative plate 8% is also reduced, illustrates that the polymer-modified binder of the present invention possesses better elasticity modulus, is reduced in cyclic process The rebound rate of Si-C composite material negative plate improves its cyclical stability.

Table 1

The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all essences in the present invention All any modification, equivalent and improvement etc. made by within refreshing and principle should all include within protection scope of the present invention.

Claims (11)

1. a kind of polymer-modified binder, it is characterised in that:The polymer-modified binder include by acrylic monomers and At least one of acrylic monomers derivative monomer carries out the polymer of polymerization formation, and the carboxylic contained by the polymer Base portion point is existed in the form of metal ion carboxylate groups.
2. polymer-modified binder according to claim 1, it is characterised in that:The metal ion carboxylate groups rub That quantity is (0.40-0.90) with the ratio between the metal ion carboxylate groups and the carboxyl total moles:1.
3. polymer-modified binder according to claim 1 or 2, it is characterised in that:The metal ion carboxylate group The metal ion in group includes at least one of the Ith race's metal ion, the IIth race's metal ion.
4. polymer-modified binder according to claim 3, it is characterised in that:The metal ion include sodium, lithium, At least one of potassium, calcium, magnesium.
5. according to 1,2, the 4 polymer-modified binder of any one of them of claim, it is characterised in that:The weight of the polymer Average molecular weight is 300,000-300 ten thousand;And/or
The acrylic monomers derivative includes 3-butenoic acid, 2 methacrylic acids, 2- penetenoic acids, 2-3 methacrylic acids, 3-3 bis- At least one of methacrylic acid.
6. a kind of preparation method of polymer-modified binder, includes the following steps:
At least one of acrylic monomers and the acrylic monomers derivative monomer are carried out to the polymerization of polymerisation formation Object;
The polymer and metal ion alkali or metal ion carbonate are subjected to neutralization reaction, neutralized contained by the polymer Part carboxyl.
7. a kind of electrode slurry, including electrode active material, binder, conductive agent and solvent, which is characterized in that the binder Including the polymer-modified binder of claim 1-5 any one of them.
8. electrode slurry according to claim 7, which is characterized in that the active material, binder, conductive agent weight Than for (94-96):(0.5-1.0):(1.0-1.5).
9. electrode slurry according to claim 7 or 8, which is characterized in that the active material is silicon, silicon-carbon composite wood At least one of material, graphite, hard carbon, carbon microspheres negative electrode active material;
The conductive agent includes at least one of carbon nanotube, Super-p, graphene.
10. a kind of electrode, including collector and the active layer that is incorporated on the collector, it is characterised in that:The active layer It is to be formed by claim 7-9 any one of them electrode slurrys.
11. a kind of lithium ion battery, it is characterised in that:Including electrode according to any one of claims 10.
CN201810201404.5A 2018-03-12 2018-03-12 Polymer-modified binder, electrode slurry and electrode and lithium ion battery CN108520958A (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104011918A (en) * 2011-10-26 2014-08-27 耐克森有限公司 Electrode composition for secondary battery cell
CN105283984A (en) * 2013-06-12 2016-01-27 Tdk株式会社 Negative electrode for lithium ion secondary batteries, and lithium ion secondary battery using same
CN107112502A (en) * 2015-01-27 2017-08-29 三洋电机株式会社 Anode for nonaqueous electrolyte secondary battery plate and the rechargeable nonaqueous electrolytic battery using the negative plate

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104011918A (en) * 2011-10-26 2014-08-27 耐克森有限公司 Electrode composition for secondary battery cell
CN105283984A (en) * 2013-06-12 2016-01-27 Tdk株式会社 Negative electrode for lithium ion secondary batteries, and lithium ion secondary battery using same
CN107112502A (en) * 2015-01-27 2017-08-29 三洋电机株式会社 Anode for nonaqueous electrolyte secondary battery plate and the rechargeable nonaqueous electrolytic battery using the negative plate

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