CN105085796A - Preparation method and application of polyacrylonitrile-acrylic acid high-molecular material - Google Patents
Preparation method and application of polyacrylonitrile-acrylic acid high-molecular material Download PDFInfo
- Publication number
- CN105085796A CN105085796A CN201410218592.4A CN201410218592A CN105085796A CN 105085796 A CN105085796 A CN 105085796A CN 201410218592 A CN201410218592 A CN 201410218592A CN 105085796 A CN105085796 A CN 105085796A
- Authority
- CN
- China
- Prior art keywords
- polyacrylonitrile
- acroleic acid
- macromolecular material
- negative electrode
- electrode active
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a preparation method for a polyacrylonitrile-acrylic acid high-molecular material. The preparation method comprises the following steps: material weighing; dispersing; initiation; emulsification; aging; etc. Through the steps, solid binder powder is prepared, and the solid binder powder is the polyacrylonitrile-acrylic acid high-molecular material. The invention also discloses a method for applying the polyacrylonitrile-acrylic acid high-molecular material in a battery. The polyacrylonitrile-acrylic acid high-molecular material does not have toxicity harmful to people, is free of the disadvantage of poor coating property of slurry, improves stability of a negative pole piece and is applicable to preparation of high power lithium ion power battery.
Description
Technical field
The invention belongs to cell manufacturing techniques field, be specifically related to a kind of polyacrylonitrile-acroleic acid macromolecular material preparation method and application in the battery thereof.
Background technology
Lithium ion battery is widely applied in telecommunications fields such as mobile phone, notebook computer, pick up cameras and occupies dominant position.Negative pole is as the important component part of lithium ion battery, and the sizing agent in its negative pole, in nearest 10 years, is paid attention to more and more widely, is the emphasis of lithium ion battery Future Development.In lithium ion battery, by high score molecular sizing agent, active substance and collector are well bonded, for the transfer of electronics provides track.Because sizing agent material is found to be reinforcement negative material, the particularly principal element of the chemical property expressive ability of high theoretical capacity such as silicon and mixture thereof; Seek the just more and more significant of efficient sizing agent.
At present, a large amount of high molecular polymers is regarded as can applying and negative electrode binder.But single a kind of monomer-polymer can exist as electroconductibility in some aspects, the deficiency of binding property and ductility, therefore polymerization forms many monomer-polymers with multifrequency nature and just becomes precondition of the present invention.Polyacrylic acid is considered to use good negative electrode binder to be approved by market, on polyacrylic acid carboxyl basis, adds itrile group functional group in polymer reaction chain, and the electroconductibility and the cancellated formation that promote tackiness agent itself are exploitation foundations of the present invention.
In the prior art, someone have employed the material of polyacrylic acid as bonding.Such as, China's patent application CN101735467B discloses the manufacture method of a kind of heat cross-linking Polypropionate as the material of bonding.Although polyacrylic acid is better than the character of other adhesive material, the simple cathode size adopting polyacrylic binder obtained on foot performance is not very stable, and the bounding force of pole piece is not very high, cathode pole piece can not be stablized and play its performance.Therefore, be necessary to develop a kind of existing polyacrylic acid characteristic, the novel high polymer copolymer adhesive of its deficiency can be assisted again, improve the performance of lithium ion battery negative further.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, a kind of existing polyacrylic acid characteristic is provided, the novel high polymer copolymer adhesive of its deficiency can be assisted again.A further object of the invention is to provide the application of above-mentioned novel high polymer copolymer adhesive in battery manufacture.
To achieve these goals, technical scheme of the present invention is, the preparation method of a kind of polyacrylonitrile-acroleic acid macromolecular material, specifically comprises the following steps:
Step 1, take material, according to the mass ratio of 68.95-69.55:0.9-0.3:0.1-0.23:10-25:5-20 take distilled water, emulsifying agent terminal hydroxy group close non-ionic additive, inorganic peroxide initiator, vinyl cyanide, vinylformic acid, used in combination in order to following steps;
Step 2, scatter stage, adds solution and the pure acrylic acid liquid of the non-ionic additive closed as emulsifying agent terminal hydroxy group, at the uniform velocity stirs, and solution is heated to 65 DEG C in distilled water;
Step 3, initiating stage, at the uniform velocity instills in the obtained solution of step 2 under the at the uniform velocity agitation condition of 65 DEG C in 30-35min by inorganic peroxide initiator solution;
Step 4, emulsifying stage, at the uniform velocity instills vinyl cyanide liquid in the obtained solution of step 3, adds rear continuation stirring 2 hours under the at the uniform velocity agitation condition of 65 DEG C in 50-70min;
Step 5, in the ageing stage, is warming up to 70 DEG C by the obtained white " milky " liquid of step 4, then stirs 1 hour post-drying and obtain adhesive solids powder, is polyacrylonitrile-acroleic acid macromolecular material.
In described step 2, the non-ionic additive that terminal hydroxy group is closed is sodium lauryl sulphate;
In described step 3, inorganic peroxide initiator is Potassium Persulphate, and now each constituent mass proportioning is 68.95-69.55:0.9-0.3:0.15:10-25:5-20
In described step 2 and 4, vinylformic acid and vinyl cyanide are the neat liquid of 99.9% purity;
Above-mentioned polyacrylonitrile-acroleic acid macromolecular material application in the battery, comprises the following steps:
Step 1, glue, obtains polyacrylonitrile-acroleic acid macromolecular material by foundation above-mentioned steps and methyl-2-pyrrolidone stirs according to the mass ratio of 5:95, is mixed into colloid;
Step 2, slurrying, mixes colloid, negative electrode active material and conductive agent, obtained slurry;
Step 3, cathode pole piece makes, and is coated with equably on a current collector by the slurry prepared, is cathode pole piece after oven dry.
In described step 2, negative electrode active material is lithium titanate, and when conductive agent is acetylene black, the mass ratio of colloid, negative electrode active material and conductive agent is 5:90:5.
In described step 2, negative electrode active material is nano-silicon, and when conductive agent is carbon fiber, the mass ratio of colloid, negative electrode active material and conductive agent is 15:80:5.
In described step 2, negative electrode active material is graphite, and when conductive agent is carbon fiber, the mass ratio of colloid, negative electrode active material and conductive agent is 8:90:2.
The present invention, by application Novel adhesive polyacrylonitrile-vinylformic acid, prepares cathode pole piece.Standard system is adopted to test for negative pole button cell method.This type material, in cathode size preparation process, can not produce the toxicity be pernicious to people, and there is not the shortcoming that slurry coating is bad.Increase the stability of cathode pole piece, be applicable to prepare high power type lithium ion power cell.
Accompanying drawing explanation
Fig. 1 is the XRD figure spectrum of the adhesive solids powder of preparation in embodiment 1.
Fig. 2 is the FT-IR collection of illustrative plates of the sizing agent powder of preparation in embodiment 1.
Fig. 3 is the discharge curve under the different multiplying of the button battery of preparation in embodiment 1.
Embodiment
Below in conjunction with drawings and Examples, the present invention is described further.
Embodiment 1:
Polyacrylonitrile-acroleic acid macromolecular material production phase step is as follows:
Step 1, the initial charge stage: by distilled water, emulsifier sodium lauryl sulfate (SDS) and monomeric acrylic take in the ratio of massfraction 69.25:0.6:20 and add reactor, according to 200rmp speed while stirring heating in water bath to 65 DEG C.
Step 2, initiating stage: add 0.15% initiator KPS according to 15ml/h speed, constant temperature continues stirring 30 minutes.
Step 3, the emulsion reaction stage: add 10% monomers acrylonitrile with 10ml/h speed.The mass ratio of vinylformic acid and vinyl cyanide is 20:10.Monomer all adds rear continuation and stirs, and continues reaction 2 hours in a kettle..
Step 4, the ageing stage: be warmed up to 70 DEG C and continue stirring 1 hour, stopped reaction.
Step 5, takes out sample: after solution being taken out from well heater cooling, the solid matter filtered out dries 24 hours in an oven, obtains adhesive solids powder.
Cathode pole piece making step is as follows:
Step 1, is dissolved in obtained adhesive solids powder in methyl-2-pyrrolidone (NMP), is prepared into the colloidal solution of mass concentration 5%; By the poly(vinylidene fluoride) (PVDF) of industrialization sizing agent, polyacrylonitrile (PAN-C) is dissolved in methyl-2-pyrrolidone (NMP), is prepared into the colloidal solution of mass concentration 5%.
Step 2, by negative electrode active material lithium titanate, conductive agent acetylene black and colloid are put into ball grinder in solid masses than the ratio of 90:5:5 and are carried out ball milling, and obtained slurry, its viscosity is at 2000-4500cP.Stirring is coated in copper foil current collector by the slurry stirred, and dries.
The pole piece of drying, according to standard button electricity making processes academic title negative pole button battery, tests its chemical property.
Can polyacrylonitrile-acroleic acid macromolecular sizing agent be a kind of unformed polymer as apparent from Fig. 1, be conducive to the contact of colloid itself and active substance, conducting material.Can C ≡ N, the contour strength key of C=O ,-O-in this band as apparent from Fig. 2, prove that polyacrylonitrile-vinylformic acid has the bond energy of high strength further; Fig. 3 is the discharge curve under the different multiplying of the button battery of preparation in embodiment 1, obviously can find out and no matter prepare the pole piece of polyacrylonitrile-vinylformic acid as sizing agent at low range 0.1C, or all show the negative pole being better than other sizing agents during high magnification 15C.
The operation steps of embodiment 2-embodiment 7 is with embodiment 1, and its difference is proportioning.Proportioning mode is as shown in the following chart:
| Embodiment | Distilled water | Emulsifying agent SDS | Initiator KPS | Vinyl cyanide | Vinylformic acid |
| 2 | 68.95 | 0.9 | 0.15 | 10 | 20 |
| 3 | 69.55 | 0.3 | 0.15 | 10 | 20 |
| 4 | 69.45 | 0.4 | 0.15 | 10 | 20 |
| 5 | 69.25 | 0.6 | 0.15 | 25 | 5 |
| 6 | 69.25 | 0.6 | 0.15 | 20 | 10 |
| 7 | 69.25 | 0.6 | 0.15 | 15 | 15 |
Embodiment 2-7 cathode pole piece preparation process and embodiment 1 completely the same, all button cells are all tested according to same test mode.
Comparative example 1-4, net result represents that its electrochemistry expression power of polyacrylonitrile-vinylformic acid that each component is prepared with the mass ratio of 69.25:0.6:0.15:10:20 is optimum.
Comparative example 1,5,6 and 7, can select when distilled water, emulsifying agent and initiator are certain, and it is best that vinyl cyanide and vinylformic acid are polymerized with the mass ratio of 10:20 its electrochemistry expressive ability of macromolecule polypropylene nitrile-vinylformic acid formed.
Macromolecular adhesive polyacrylonitrile-the vinylformic acid prepared with the best proportion measured, for colloid, prepares the cathode pole piece of different activities material.Its method preparing cathode pole piece with embodiment 1, the material mass such as following table of each pole piece:
Above embodiments of the invention are explained in detail, above-mentioned embodiment is only optimum embodiment of the present invention, but the present invention is not limited to above-described embodiment, in the ken that those of ordinary skill in the art possess, various change can also be made under the prerequisite not departing from present inventive concept.
Claims (8)
1. a preparation method for polyacrylonitrile-acroleic acid macromolecular material, is characterized in that comprising the following steps:
Step 1, take material, according to the mass ratio of 68.95-69.55:0.9-0.3:0.1-0.23:10-25:5-20 take distilled water, emulsifying agent terminal hydroxy group close non-ionic additive, inorganic peroxide initiator, vinyl cyanide, vinylformic acid, used in combination in order to following steps;
Step 2, scatter stage, adds solution and the pure acrylic acid liquid of the non-ionic additive closed as emulsifying agent terminal hydroxy group, at the uniform velocity stirs, and solution is heated to 65 DEG C in distilled water;
Step 3, initiating stage, at the uniform velocity instills in the obtained solution of step 2 under the at the uniform velocity agitation condition of 65 DEG C in 30-35min by inorganic peroxide initiator solution;
Step 4, emulsifying stage, at the uniform velocity instills vinyl cyanide liquid in the obtained solution of step 3, adds rear continuation stirring 2 hours under the at the uniform velocity agitation condition of 65 DEG C in 50-70min;
Step 5, in the ageing stage, is warming up to 70 DEG C by the obtained white " milky " liquid of step 4, then stirs 1 hour post-drying and obtain adhesive solids powder, is polyacrylonitrile-acroleic acid macromolecular material.
2. the preparation method of a kind of polyacrylonitrile-acroleic acid macromolecular material as claimed in claim 1, is characterized in that the non-ionic additive that in step 2, terminal hydroxy group is closed is sodium lauryl sulphate.
3. the preparation method of a kind of polyacrylonitrile-acroleic acid macromolecular material as claimed in claim 1, it is characterized in that in step 3, inorganic peroxide initiator is Potassium Persulphate, now each constituent mass proportioning is 68.95-69.55:0.9-0.3:0.15:10-25:5-20.
4. the preparation method of a kind of polyacrylonitrile-acroleic acid macromolecular material as claimed in claim 1, is characterized in that in step 2 and 4, and vinylformic acid and vinyl cyanide are the neat liquid of 99.9% purity.
5. polyacrylonitrile according to claim 1-acroleic acid macromolecular material application in the battery, is characterized in that comprising the following steps:
Step 1, glue, obtains polyacrylonitrile-acroleic acid macromolecular material by foundation above-mentioned steps and methyl-2-pyrrolidone stirs according to the mass ratio of 5:95, is mixed into colloid;
Step 2, slurrying, mixes colloid, negative electrode active material and conductive agent, obtained slurry;
Step 3, cathode pole piece makes, and is coated with equably on a current collector by the slurry prepared, is cathode pole piece after oven dry.
6. polyacrylonitrile-acroleic acid macromolecular material application in the battery as claimed in claim 5, it is characterized in that in step 2, negative electrode active material is lithium titanate, and when conductive agent is acetylene black, the mass ratio of colloid, negative electrode active material and conductive agent is 5:90:5.
7. polyacrylonitrile-acroleic acid macromolecular material application in the battery as claimed in claim 5, it is characterized in that in step 2, negative electrode active material is nano-silicon, and when conductive agent is carbon fiber, the mass ratio of colloid, negative electrode active material and conductive agent is 15:80:5.
8. polyacrylonitrile-acroleic acid macromolecular material application in the battery as claimed in claim 5, it is characterized in that in step 2, negative electrode active material is graphite, and when conductive agent is carbon fiber, the mass ratio of colloid, negative electrode active material and conductive agent is 8:90:2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410218592.4A CN105085796B (en) | 2014-05-22 | 2014-05-22 | Polyacrylonitrile acroleic acid macromolecular material preparation method and its application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410218592.4A CN105085796B (en) | 2014-05-22 | 2014-05-22 | Polyacrylonitrile acroleic acid macromolecular material preparation method and its application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105085796A true CN105085796A (en) | 2015-11-25 |
| CN105085796B CN105085796B (en) | 2017-09-29 |
Family
ID=54567188
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410218592.4A Active CN105085796B (en) | 2014-05-22 | 2014-05-22 | Polyacrylonitrile acroleic acid macromolecular material preparation method and its application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105085796B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106633130A (en) * | 2016-11-29 | 2017-05-10 | 江西师范大学 | High-breakdown-strength polyimide thin film and preparation method thereof |
| CN107043438A (en) * | 2016-11-29 | 2017-08-15 | 江西师范大学 | Oleic acid acrylonitrile copolymer and preparation method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020034686A1 (en) * | 2000-07-26 | 2002-03-21 | Zeon Corporation | Binder for electrode for lithium ion secondary battery, and utilization thereof |
| CN101023543A (en) * | 2004-09-22 | 2007-08-22 | 日立化成工业株式会社 | Binder resin composition for nonaqueous electrolyte energy device electrode, non-aqueous electrolyte energy device electrode, and nonaqueous electrolyte energy device |
| CN101926032A (en) * | 2008-04-16 | 2010-12-22 | Lg化学株式会社 | Anode composition comprising acrylonitrile-acrylic acid copolymer as binder, method for preparing anode composition and lithium secondary battery using anode composition |
| JP2012238489A (en) * | 2011-05-12 | 2012-12-06 | Sumitomo Chemical Co Ltd | Electrode binder |
| JP2013093297A (en) * | 2011-05-12 | 2013-05-16 | Sumitomo Chemical Co Ltd | Binder for electrode, electrode coating, electrode and lithium ion secondary battery |
| CN103173161A (en) * | 2013-03-08 | 2013-06-26 | 东莞新能源科技有限公司 | Preparation method of lithium ion battery cathode sheet adhesive emulsion |
-
2014
- 2014-05-22 CN CN201410218592.4A patent/CN105085796B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020034686A1 (en) * | 2000-07-26 | 2002-03-21 | Zeon Corporation | Binder for electrode for lithium ion secondary battery, and utilization thereof |
| CN101023543A (en) * | 2004-09-22 | 2007-08-22 | 日立化成工业株式会社 | Binder resin composition for nonaqueous electrolyte energy device electrode, non-aqueous electrolyte energy device electrode, and nonaqueous electrolyte energy device |
| CN101926032A (en) * | 2008-04-16 | 2010-12-22 | Lg化学株式会社 | Anode composition comprising acrylonitrile-acrylic acid copolymer as binder, method for preparing anode composition and lithium secondary battery using anode composition |
| JP2012238489A (en) * | 2011-05-12 | 2012-12-06 | Sumitomo Chemical Co Ltd | Electrode binder |
| JP2013093297A (en) * | 2011-05-12 | 2013-05-16 | Sumitomo Chemical Co Ltd | Binder for electrode, electrode coating, electrode and lithium ion secondary battery |
| CN103173161A (en) * | 2013-03-08 | 2013-06-26 | 东莞新能源科技有限公司 | Preparation method of lithium ion battery cathode sheet adhesive emulsion |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106633130A (en) * | 2016-11-29 | 2017-05-10 | 江西师范大学 | High-breakdown-strength polyimide thin film and preparation method thereof |
| CN107043438A (en) * | 2016-11-29 | 2017-08-15 | 江西师范大学 | Oleic acid acrylonitrile copolymer and preparation method thereof |
| CN106633130B (en) * | 2016-11-29 | 2019-05-24 | 江西师范大学 | High breakdown strength Kapton and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105085796B (en) | 2017-09-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6641400B2 (en) | Electrode binder composition for lithium ion storage device | |
| CN105504169B (en) | A kind of binding agent for lithium ion battery | |
| CN106281147B (en) | A kind of water base binders for electrodes and preparation method | |
| CN100418257C (en) | Composite binder for an electrode with dispersants chemically bound | |
| JP2018078124A (en) | Aqueous binder composition for lithium ion electrical storage devices | |
| CN106433530A (en) | Water-based electrode bonding agent for sulfur positive pole and preparing method | |
| CN108417836A (en) | A kind of binders for electrodes of new type lithium ion battery and preparation method thereof | |
| TWI746131B (en) | A binder for battery, a negative electrode of lithium ion battery, and a lithium ion battery | |
| CN1195036C (en) | Water adhesive for electrode material of secondary lithium ion battery and its preparing process | |
| CN107325225B (en) | Negative electrode of lithium ion battery aqueous binder and preparation method thereof | |
| CN109755579B (en) | Preparation method of positive electrode composite conductive adhesive for lithium ion battery | |
| CN104530276B (en) | A kind of preparation method of the special Kynoar of lithium battery binding agent | |
| CN111635478A (en) | Low-impedance binder and preparation method and application thereof | |
| CN101045762B (en) | Organic inorganic composite polymer electrolyte and preparation method and application thereof | |
| CN100524936C (en) | Micro joint gel state lithium ion battery polymer electrolyte film and its making method | |
| CN109935830B (en) | Preparation method of lithium ion battery silicon-carbon negative electrode plate based on modified gelatin binder | |
| CN103351448B (en) | A kind of High-temperature resistance lithium ion secondary battery adhesive and preparation method | |
| CN114573746B (en) | High-lithium-content high-molecular-weight lithium acrylate emulsion and preparation method and application thereof | |
| CN117089315B (en) | Aqueous lithium battery polyimide adhesive, preparation method thereof and lithium battery pole piece | |
| CN105085796A (en) | Preparation method and application of polyacrylonitrile-acrylic acid high-molecular material | |
| WO2019167730A1 (en) | Slurry composition for lithium ion secondary battery, and electrode for lithium ion secondary battery | |
| CN109721713B (en) | High-conductivity lithium ion battery positive electrode slurry and preparation method thereof | |
| CN105957993A (en) | Preparation method for thermal-crosslinking polymer electrolyte membrane for lithium battery | |
| JP6061563B2 (en) | Aqueous electrode binder for secondary battery | |
| CN108172836A (en) | The preparation method of polyvinylidene fluoride modified composite conducting binding agent |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20221020 Address after: No.8, Huancheng Road, Fengcheng Town, Tianzhu County, Qiandongnan Miao and Dong Autonomous Prefecture, Guizhou 556600 Patentee after: Wu Weiyue Address before: 100176 Aerospace Science Park, No. 6, Jinxiu Street, Beijing Economic and Technological Development Zone, Daxing District, Beijing Patentee before: BEIJING WANYUAN INDUSTRY Co.,Ltd. |