CN105085796B - Polyacrylonitrile acroleic acid macromolecular material preparation method and its application - Google Patents
Polyacrylonitrile acroleic acid macromolecular material preparation method and its application Download PDFInfo
- Publication number
- CN105085796B CN105085796B CN201410218592.4A CN201410218592A CN105085796B CN 105085796 B CN105085796 B CN 105085796B CN 201410218592 A CN201410218592 A CN 201410218592A CN 105085796 B CN105085796 B CN 105085796B
- 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.)
- Active
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 kind of preparation method of polyacrylonitrile acroleic acid macromolecular material, including weigh material --- scattered --- step such as initiation --- emulsification --- ageing, as obtained adhesive solids powder, polyacrylonitrile acroleic acid macromolecular material.The invention also discloses a kind of application process of utilization above-mentioned material in the battery.The toxicity being pernicious to people will not be produced, in the absence of the bad shortcoming of slurry coating, increases the stability of cathode pole piece, it is adaptable to prepare high power type lithium ion electrokinetic cell.
Description
Technical field
The invention belongs to cell manufacturing techniques field, and in particular to prepared by a kind of polyacrylonitrile-acroleic acid macromolecular material
Method and its application in the battery.
Background technology
Lithium ion battery is widely applied and occupied in the telecommunications such as mobile phone, notebook computer, video camera field
Leading position.Negative pole is as the important component of lithium ion battery, and the adhesive in its negative pole is in nearest 10 years, more
Widely paid attention to get over, be the emphasis of lithium ion battery Future Development.In lithium ion battery, by the molecular glue of high score
Glutinous agent bonds active material with collector well, and track is provided for the transfer of electronics.Because gluing agent material is found to be
Strengthen negative material, the principal element of the chemical property expressive ability of particularly high theoretical capacity such as silicon and its compound；
Seek the just increasingly significant of efficient adhesive.
At present, substantial amounts of high molecular polymer is considered as to apply and negative electrode binder.But a kind of single monomer polymerization
Thing can have the deficiency of such as electric conductivity, cohesive and ductility in some aspects, therefore polymerization forms many with multifrequency nature
Monomer-polymer just turns into the precondition of the present invention.Polyacrylic acid is considered as using good negative electrode binder by market
Accreditation, on the basis of polyacrylic acid carboxyl, adds itrile group functional group, the electric conductivity of lifting adhesive in itself in polymer reaction chain
Formation with network structure is the exploitation foundation of the present invention.
In the prior art, someone employs polyacrylic acid as the material of bonding.For example, China's patent application
CN101735467B discloses a kind of heat cross-linking Polypropionate as the manufacture method of the material of bonding.Although polyacrylic acid ratio
The property of other adhesive materials will get well, but using cathode size made from polyacrylic binder, performance is not on foot merely
Very stable, the bonding force of pole piece is not very high, cathode pole piece is played its performance from stablizing.Therefore, it is necessary to develop one
Existing polyacrylic acid characteristic is planted, the novel high polymer copolymer adhesive that can aid in it not enough again further improves lithium-ion electric
The performance of pond negative pole.
The content of the invention
The purpose of the present invention is to overcome the deficiencies in the prior art there is provided a kind of existing polyacrylic acid characteristic, and it can be aided in again
Not enough novel high polymer copolymer adhesive.It is a still further object of the present invention to provide the bonding of above-mentioned novel high polymer copolymer
Application of the agent in battery manufacture.
To achieve these goals, the technical scheme is that, a kind of system of polyacrylonitrile-acroleic acid macromolecular material
Preparation Method, specifically includes following steps：
Step 1, material is weighed, according to 68.95-69.55：0.9-0.3：0.1-0.23：10-25：5-20 mass ratio claims
Distilled water, non-ionic additive, inorganic peroxide initiator, acrylonitrile, the acrylic acid of the closing of emulsifying agent terminal hydroxy group are taken, in case with
Lower step is used in mixed way；
Step 2, scatter stage, added in distilled water as emulsifying agent terminal hydroxy group close non-ionic additive solution and
Pure acrylic acid liquid, is at the uniform velocity stirred, and solution is heated into 65 DEG C；
Step 3, initiating stage, by inorganic peroxide initiator in 30-35min under 65 DEG C of at the uniform velocity stirring condition
Solution is at the uniform velocity instilled in solution made from step 2；
Step 4, emulsifying stage, at the uniform velocity instills acrylonitrile liquid in 50-70min under 65 DEG C of at the uniform velocity stirring condition
Continue to stir 2 hours in solution made from step 3, after addition；
Step 5, the ageing stage, the obtained white milky liquid of step 4 is warming up to 70 DEG C, is stirred for drying after 1 hour
Do to obtain adhesive solids powder, as polyacrylonitrile-acroleic acid macromolecular material.
In the step 2, the non-ionic additive of terminal hydroxy group closing is lauryl sodium sulfate；
In the step 3, inorganic peroxide initiator is potassium peroxydisulfate, and now each component quality proportioning is 68.95-
69.55：0.9-0.3：0.15：10-25：5-20
In the step 2 and 4, acrylic acid and the neat liquid that acrylonitrile is 99.9% purity；
Above-mentioned polyacrylonitrile-the application of acroleic acid macromolecular material in the battery, comprises the following steps：
Step 1, glue, will be made polyacrylonitrile-acroleic acid macromolecular material and methyl pyrrolidone according to above-mentioned steps
According to 5:95 mass ratio stirring, is mixed into colloid；
Step 2, slurrying, colloid, negative electrode active material and conductive agent are mixed, and slurry is made；
Step 3, cathode pole piece is made, and the slurry prepared is equably applied on a current collector, is negative pole after drying
Pole piece.
In the step 2, negative electrode active material is lithium titanate, when conductive agent is acetylene black, colloid, negative electrode active material and
The mass ratio of conductive agent is 5：90：5.
In the step 2, negative electrode active material is nano-silicon, when conductive agent is carbon fiber, colloid, negative electrode active material and
The mass ratio of conductive agent is 15：80：5.
In the step 2, negative electrode active material is graphite, when conductive agent is carbon fiber, colloid, negative electrode active material and is led
The mass ratio of electric agent is 8：90：2.
The present invention prepares cathode pole piece by applying Novel adhesive polyacrylonitrile-acrylic acid.Negative pole is prepared using standard
Button cell method is tested.This new material will not produce the toxicity being pernicious to people, no in cathode size preparation process
Have the shortcomings that slurry coating is bad.Increase the stability of cathode pole piece, it is adaptable to prepare high power type lithium ion power electric
Pond.
Brief description of the drawings
Fig. 1 is the XRD spectrum of the adhesive solids powder prepared in embodiment 1.
Fig. 2 is the FT-IR collection of illustrative plates of the adhesive powder prepared in embodiment 1.
Fig. 3 is the discharge curve under the different multiplying of the button battery prepared in embodiment 1.
Embodiment
The present invention is described further with reference to the accompanying drawings and examples.
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 are pressed
Mass fraction 69.25:0.6:20 ratio is weighed and adds reactor, and according to 200rmp speed, heating water bath is arrived while stirring
65℃。
Step 2, initiating stage：0.15% initiator KPS is added according to 15ml/h speed, constant temperature continues to stir 30 minutes.
Step 3, the emulsion reaction stage：10% monomers acrylonitrile is added with 10ml/h speed.The matter of acrylic acid and acrylonitrile
Amount is than being 20：10.Monomer continues to stir after all adding, and continues to react 2 hours in a kettle..
Step 4, the ageing stage：It is warming up to 70 DEG C to continue to stir 1 hour, stops reaction.
Step 5, sample is taken out：Solution is taken out after cooling from heater, the solid matter filtered out dries in an oven
It is dry 24 hours, obtain adhesive solids powder.
Cathode pole piece making step is as follows：
Step 1, obtained adhesive solids powder is dissolved in methyl pyrrolidone (NMP), is prepared into mass concentration 5%
Colloidal solution；The polyvinylidene fluoride (PVDF) of adhesive will be industrialized, polyacrylonitrile (PAN-C) is dissolved in methyl pyrrolidone
(NMP) in, it 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 compare 90 by solid masses：5：5 ratio
It is put into ball grinder and carries out ball milling, slurry is made, its viscosity is in 2000-4500cP.The slurry stirred is coated in copper by stirring
On paper tinsel collector, drying.
The pole piece of drying tests its chemical property according to the electric manufacturing process academic title's negative pole button battery of standard button.
From Fig. 1 this it appears that polyacrylonitrile-acroleic acid macromolecular adhesive is a kind of unformed macromolecule, favorably
In the contact of colloid with active material, conductive materials in itself.C ≡ N, C=O ,-O- etc. can be will become apparent from this band from Fig. 2
High intensity key, further proves that polyacrylonitrile-acrylic acid has the bond energy of high intensity；Fig. 3 is the button-shaped electricity for preparing in embodiment 1
Discharge curve under the different multiplying in pond, it can be clearly seen that prepare polyacrylonitrile-acrylic acid as adhesive pole piece no matter
The negative pole better than other adhesives is all showed in low range 0.1C, or during high magnification 15C.
The operating procedure be the same as Example 1 of embodiment 2- embodiments 7, it, which is distinguished, is to match.Proportioning mode is as shown in the following chart：
| Embodiment | Distilled water | Emulsifying agent SDS | Initiator KPS | Acrylonitrile | Acrylic 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 pieces preparation process and embodiment 1 are completely the same, and all button cells are all according to same test
Mode is tested.
Comparative example 1-4, final result represents each component with 69.25:0.6:0.15:10:Prepared by 20 mass ratio
Its electrochemistry expression power of polyacrylonitrile-acrylic acid is optimal.
Comparative example 1,5,6 and 7, can be selected in distilled water, emulsifying agent and certain initiator, acrylonitrile with
Acrylic acid is with 10:It is best that 20 mass ratio polymerize the macromolecule polypropylene to be formed nitrile-acrylic acid its electrochemistry expressive ability.
Macromolecular adhesive polyacrylonitrile-acrylic acid using the best proportion preparation of measure prepares different activities as colloid
The cathode pole piece of material.It prepares the method be the same as Example 1 of cathode pole piece, the material mass such as following table of each pole piece：
Embodiments of the invention are explained in detail above, above-mentioned embodiment is only most highly preferred embodiment of the invention,
, can also be in the knowledge that those of ordinary skill in the art possess but the present invention is not limited to above-described embodiment
Do not depart from the premise of present inventive concept that various changes can be made.
Claims (7)
1. the preparation method of a kind of polyacrylonitrile-acroleic acid macromolecular material, it is characterised in that comprise the following steps：
Step 1, material is weighed, according to 68.95-69.55：0.9-0.3：0.1-0.23：10-25：5-20 mass ratio weighs steaming
Distilled water, emulsifier sodium lauryl sulfate, inorganic peroxide initiator, acrylonitrile, acrylic acid, in case following steps mixing makes
With；
Step 2, scatter stage, adds the solution and pure acrylic acid liquid as emulsifier sodium lauryl sulfate in distilled water
Body, is at the uniform velocity stirred, and solution is heated into 65 DEG C；
Step 3, initiating stage, by inorganic peroxide initiator solution in 30-35min under 65 DEG C of at the uniform velocity stirring condition
At the uniform velocity instill in solution made from step 2；
Step 4, emulsifying stage, step is at the uniform velocity instilled under 65 DEG C of at the uniform velocity stirring condition in 50-70min by acrylonitrile liquid
Continue to stir 2 hours in solution made from 3, after addition；
Step 5, the ageing stage, the obtained white milky liquid of step 4 is warming up to 70 DEG C, dried after being stirred for 1 hour
Adhesive solids powder, as polyacrylonitrile-acroleic acid macromolecular material.
2. a kind of preparation method of polyacrylonitrile-acroleic acid macromolecular material as claimed in claim 1, it is characterised in that step
Inorganic peroxide initiator is potassium peroxydisulfate in 3, and now each component quality proportioning is 68.95-69.55：0.9-0.3：0.15：
10-25：5-20.
3. a kind of preparation method of polyacrylonitrile-acroleic acid macromolecular material as claimed in claim 1, it is characterised in that step
In 2 and 4, acrylic acid and the neat liquid that acrylonitrile is 99.9% purity.
4. polyacrylonitrile-acroleic acid macromolecular material prepared by a kind of preparation method described in claim 1 in the battery should
With, it is characterised in that comprise the following steps：
Step 1, glue, will be made polyacrylonitrile-acroleic acid macromolecular material and crassitude according to step in claim 1
Ketone is according to 5:95 mass ratio stirring, is mixed into colloid；
Step 2, slurrying, colloid, negative electrode active material and conductive agent are mixed, and slurry is made；
Step 3, cathode pole piece is made, and the slurry prepared is equably applied on a current collector, is cathode pole piece after drying.
5. the polyacrylonitrile as claimed in claim 4-application of acroleic acid macromolecular material in the battery, it is characterised in that in step
In rapid 2, negative electrode active material is lithium titanate, when conductive agent is acetylene black, the mass ratio of colloid, negative electrode active material and conductive agent
For 5：90：5.
6. the polyacrylonitrile as claimed in claim 4-application of acroleic acid macromolecular material in the battery, it is characterised in that in step
In rapid 2, negative electrode active material is nano-silicon, when conductive agent is carbon fiber, the mass ratio of colloid, negative electrode active material and conductive agent
For 15：80：5.
7. the polyacrylonitrile as claimed in claim 4-application of acroleic acid macromolecular material in the battery, it is characterised in that in step
In rapid 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 CN105085796A (en) | 2015-11-25 |
| CN105085796B true 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) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106633130B (en) * | 2016-11-29 | 2019-05-24 | 江西师范大学 | High breakdown strength Kapton and preparation method thereof |
| CN107043438B (en) * | 2016-11-29 | 2019-04-05 | 江西师范大学 | Oleic acid-acrylonitrile copolymer and preparation method thereof |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6656633B2 (en) * | 2000-07-26 | 2003-12-02 | Zeon Corporation | Binder for electrode for lithium ion secondary battery, and utilization thereof |
| JP4636444B2 (en) * | 2004-09-22 | 2011-02-23 | 日立化成工業株式会社 | Binder resin composition for non-aqueous electrolyte system energy device electrode, non-aqueous electrolyte system energy device electrode, and non-aqueous electrolyte system energy device |
| KR101041829B1 (en) * | 2008-04-16 | 2011-06-17 | 주식회사 엘지화학 | Anode material including polyacrylonitrile-acrylic acid, and binder, manufacture of the same and rechargeable lithium battery comprising the same |
| JP2013093297A (en) * | 2011-05-12 | 2013-05-16 | Sumitomo Chemical Co Ltd | Binder for electrode, electrode coating, electrode and lithium ion secondary battery |
| JP2012238489A (en) * | 2011-05-12 | 2012-12-06 | Sumitomo Chemical Co Ltd | Electrode binder |
| CN103173161B (en) * | 2013-03-08 | 2016-08-03 | 东莞新能源科技有限公司 | A kind of preparation method of lithium ion battery cathode sheet adhesive emulsion |
-
2014
- 2014-05-22 CN CN201410218592.4A patent/CN105085796B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN105085796A (en) | 2015-11-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105504169B (en) | A kind of binding agent for lithium ion battery | |
| CN106433530B (en) | A kind of sulphur cathode water base binders for electrodes and preparation method | |
| CN107078300B (en) | High-molecular compound, intermediate composition, negative electrode, electrical storage device, negative electrode slurry and its manufacturing method | |
| CN106281147B (en) | A kind of water base binders for electrodes and preparation method | |
| TWI332284B (en) | A battery electrode paste composition containing modified maleimides | |
| CN108417836B (en) | Electrode binder of lithium ion battery and preparation method thereof | |
| CN104882612B (en) | A kind of lithium ion battery of binding agent and the application binding agent | |
| CN106450327B (en) | A method of irradiation improves lithium battery Kynoar gluing performance | |
| WO2015098050A1 (en) | Slurry composition for negative electrodes of lithium ion secondary batteries, negative electrode for lithium ion secondary batteries, and lithium ion secondary battery | |
| CN1195036C (en) | Water adhesive for electrode material of secondary lithium ion battery and its preparing process | |
| CN1765025A (en) | Composite binder for an electrode with dispersants chemically bound | |
| CN107325225B (en) | Negative electrode of lithium ion battery aqueous binder and preparation method thereof | |
| JP2016091987A (en) | Negative electrode film and lithium ion battery as application thereof | |
| CN109904454B (en) | Silicon-containing polymer binder, preparation method thereof and application thereof in silicon-based electrode lithium ion battery | |
| CN105018001A (en) | Aqueous binder used for lithium ion batteries, positive and negative electrode plates and coating membrane | |
| CN105576247A (en) | Modified ocean polysaccharide macromolecule lithium ion battery binder and preparing method and application thereof | |
| TW201205946A (en) | Binder resin composition and slurry composition containing the same for electrode of nonaqueous electrolyte battery, electrode and battery | |
| CN108701832A (en) | The manufacturing method of high-molecular compound, intermediate constituent, negative electrode, electrical storage device, negative electrode slurry, the manufacturing method of high-molecular compound and negative electrode | |
| CN109950543B (en) | Current collector suitable for lithium ion battery electrode material and preparation and application thereof | |
| CN101045762B (en) | Organic inorganic composite polymer electrolyte and preparation method and application thereof | |
| He et al. | Water‐soluble binder PAAL i with terpene resin emulsion as tackifier for L i FePO 4 cathode | |
| CN111554889A (en) | polyimide/MXene composite material and preparation and application thereof | |
| CN103351448B (en) | A kind of High-temperature resistance lithium ion secondary battery adhesive and preparation method | |
| CN105085796B (en) | Polyacrylonitrile acroleic acid macromolecular material preparation method and its application | |
| CN111712952A (en) | Slurry composition for lithium ion secondary battery and electrode for lithium ion secondary battery |
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 |
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. |
|
| TR01 | Transfer of patent right |