CN1296430C - Colloidal polymer electrolyte and preparation process thereof - Google Patents
Colloidal polymer electrolyte and preparation process thereof Download PDFInfo
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- CN1296430C CN1296430C CNB2004100607006A CN200410060700A CN1296430C CN 1296430 C CN1296430 C CN 1296430C CN B2004100607006 A CNB2004100607006 A CN B2004100607006A CN 200410060700 A CN200410060700 A CN 200410060700A CN 1296430 C CN1296430 C CN 1296430C
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- colloidal state
- electrolyte
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Abstract
The present invention relates to a colloidal polymer electrolyte and a preparation process thereof. The present invention has the basic principles that acrylate and derivatives of the acrylate are used as monomers, an electrolyte solution and the monomers are mixed to make a uniform and stable precursor solution with moderate viscosity; an initiator is added to cause the acrylate to generate a chemical crosslink reaction, and then, a polymer network structure is formed; a liquid electrolyte solution is fixed in the microstructure of polymer networks, and thereby, the colloidal polymer electrolyte is obtained. Compared with a liquid electrolyte, the made polymer electrolyte has high conductivity and good mechanical strength, easily realizes the conception of fully solid state cells and realizes the special design of miniaturization, thinning, etc. of chemical electric sources. The present invention can be generally used for various cell systems, such as zinc-air cells, zinc-nickel cells, hydrogen-nickel cells, lead-acid cells, etc.
Description
Technical field
The present invention is a kind of colloidal state polymer ionogen and preparation method thereof, belongs to technical field of chemical power.
Background technology
Polymer dielectric can prevent battery leakage, be easy to realize the conception of all-solid-state battery, help realizing particular design such as chemical power source microminiaturization, slimming simultaneously, greatly attracted the applied research in field of chemical power source, at the beginning of the nineties, begin to occur the commercialization report of polymer electrolyte battery.In addition, polymer dielectric causes fields such as colour developing, electrochemical sensor at ultracapacitor, electricity potential using value also causes people's very big interest, and has carried out applied research widely for this reason.
Some investigators have carried out unremitting effort for the application that realizes polymer dielectric.Research and develop out PEO-KOH, P (ECH-co-EO)-KOH and PVA-KOH-H
2O alkalescence colloidal state polymer electrolyte system, at room temperature, though these systems have mechanical property preferably, ionic conductivity all can only reach 10
-3S.cm
-1Compare with the KOH aqueous solution, the specific conductivity of these polymer dielectrics is too wide in the gap, has obviously restricted the big current capacity of battery.Therefore, a kind of application development with electric conductivity height, polymer electrolytic confrontation chemical power source that physical strength is good of exploitation plays an important role.
Summary of the invention:
The objective of the invention is to develop a kind of colloidal state polymer ionogen that has high conductivity, better physical strength, do not have the electrolytic solution that flows.
Technical scheme of the present invention is: the colloidal state polymer ionogen, it is made of liquid electrolyte solution and colloidal state polymer, it is characterized in that: liquid electrolyte solution is fixed in the network microstructure of colloidal state polymer, the two mixes initiated polymerization and forms colloidal state polymer by acrylate and/or its derivatives monomer and initiator, or mixes initiated polymerization by acrylate and/or its derivatives monomer, linking agent and initiator three and form.
Aforesaid colloidal state polymer ionogen is characterized in that:
A, colloidal state polymer electrolyte precursor liquid solution are the mixing solutions of polymer monomer and alkaline electrolyte, or the mixing solutions of polymer monomer, linking agent and alkaline electrolyte, wherein:
Polymer monomer is acrylate and/or its derivative: its structure is CH
2=C (R
1) COOM, wherein R
1The structure of group is H or CH
3, M is H
+Or NH
4 +, basic metal or alkaline-earth metal, the overall mass fraction of shared mixing solutions is 5～50wt%;
Linking agent is acrylamide and/or N, N '-methylene-bisacrylamide, and the overall mass fraction of shared mixing solutions is greater than 0～1.0wt%;
Alkaline electrolyte solution can be one of basic solution, acidic solution or neutral solution, and concentration is 1～10mol/L, and the overall mass fraction of shared mixing solutions is 50～95wt%;
B, the initiator that is used for initiated polymerization are polyreaction initiators commonly used, can be a kind of of hydrogen peroxide, persulphate, persulphate and sulphite or thiosulphate, and its consumption umber is 0.01～1.0wt% of mixing solutions oeverall quality;
The summation of each component is 100wt%.
Aforesaid colloidal state polymer ionogen is characterized in that described basic metal is K
+Or Na
+Or Li
+, alkaline-earth metal is Mg or Ca or Ba ion.
Aforesaid colloidal state polymer ionogen is characterized in that described basic solution can be KOH, NaOH, LiOH, Ba (OH)
2One of; Acidic solution can be HCl, HNO
3, H
2SO
4One of; Neutral solution can be NaCl, KCl, MgCl
2One of.
A kind of colloidal state polymer electrolyte preparation method, it is characterized in that with acrylate and/or its derivative be monomer, with monomer and the two mixing of electrolyte solution or monomer, electrolyte solution and linking agent three mixing, make the precursor solution of homogeneous, stable, modest viscosity, add initiator then, make monomer generation chemical crosslink reaction, form polymer network structure, liquid electrolyte solution is fixed in the microstructure of polymer network, thereby obtains the colloidal polymer dielectric.Prepared polymer dielectric is compared with liquid electrolyte, and (its room-temperature conductivity can be up to 0.5S.cm to have suitable substantially specific conductivity
-1).
Aforesaid preparation method is characterized in that:
A, colloidal state polymer electrolyte precursor liquid solution are the mixing solutions of polymer monomer and alkaline electrolyte, or the mixing solutions of polymer monomer, linking agent and alkaline electrolyte, wherein:
Polymer monomer is acrylate and/or its derivative: its structure is CH
2=C (R
1) COOM, wherein R
1The structure of group is H or CH
3, M is H
+Or NH
4 +, basic metal or alkaline-earth metal, the overall mass fraction of shared mixing solutions is 5～50wt%;
Linking agent is acrylamide and/or N, N '-methylene-bisacrylamide, and the overall mass fraction of shared mixing solutions is greater than 0～1.0wt%;
Alkaline electrolyte solution can be one of basic solution, acidic solution or neutral solution, and concentration is 1～10mol/L, and the overall mass fraction of shared mixing solutions is 50～95wt%;
B, the initiator that is used for initiated polymerization are polyreaction initiators commonly used, can be a kind of of hydrogen peroxide, persulphate, persulphate and sulphite or thiosulphate, and its consumption umber is 0.01～1.0wt% of mixing solutions oeverall quality;
The summation of each component is 100wt%.
Aforesaid colloidal state polymer electrolyte preparation method is characterized in that described basic metal is K
+Or Na
+Or Li
+, alkaline-earth metal is Mg or Ca or Ba ion.
Aforesaid colloidal state polymer electrolyte preparation method is characterized in that described basic solution can be KOH, NaOH, LiOH, Ba (OH)
2One of; Acidic solution can be HCl, HNO
3, H
2SO
4One of; Neutral solution can be NaCl, KCl, MgCl
2One of.
Aforesaid colloidal state polymer electrolyte preparation method is characterized in that 10～80 ℃ of polymer monomer polymerization temperatures.
Aforesaid colloidal state polymer electrolyte preparation method is characterized in that with concentration being that the electrolyte solution of 1～10mol/L is added dropwise in the mixed solution of polymer monomer and linking agent gradually.
The invention has the advantages that and adopt polymer monomer polymerization in electrolyte solution to form the colloidal state polymer ionogen.Compare with liquid electrolyte, prepared polymer dielectric has high specific conductivity, physical strength preferably.Because the colloidal state polymer electrode has and does not have obviously flow electric liquid and special water retaining function, can prevent leakage in damp atmosphere, and it is dry under dry environment, be easy to realize the conception of all-solid-state battery and realize particular design such as chemical power source microminiaturization, slimming, can be widely used in multiple battery systems such as zinc and air cell, zinc-nickel cell, Ni-H cell, lead-acid cell.
Concrete embodiment
Embodiment 1 colloidal state polymer preparation of electrolyte 1
In following ratio preparation mixed solution, after stirring, as the polymer dielectric precursor solution.
Vinylformic acid: 12.5%
Linking agent (N, N '-methylene-bis (acrylamide)): 0.06%
KOH solution (10mol/L): 87.44%
Under agitation, in the polymer dielectric precursor solution, add 50mg 4% initiator (Na
2SO
3+ K
2S
2O
81: 1wt) solution, treat promptly to form the colloidal state polymer ionogen after the solution polymerization.
Embodiment 2 colloidal state polymer preparation of electrolyte 2
In following ratio preparation mixed solution, after stirring, as the polymer dielectric precursor solution.
Vinylformic acid: 12.5%
H
2SO
4Solution (4mol/L): 87.5%
Under agitation, in the polymer dielectric precursor solution, add 50mg 4% initiator (K
2S
2O
8) solution, treat promptly to form the colloidal state polymer ionogen after the solution polymerization.
Embodiment 3, colloidal state polymer zinc and air cell preparation 3
In following ratio preparation mixed solution, after stirring, as the polymer dielectric precursor solution.
Vinylformic acid: 15%
Linking agent (N, N '-methylene-bis (acrylamide)): 0.06%
NH
4Cl solution (2mol/L): 84.94%
Under agitation, in the polymer dielectric precursor solution, add 50mg 4% initiator ((NH
4)
2S
2O
8) solution, treat promptly to form the colloidal state polymer ionogen after the solution polymerization.
Claims (7)
1, colloidal state polymer ionogen, it is made of liquid electrolyte solution and colloidal state polymer, it is characterized in that: liquid electrolyte solution is fixed in the network microstructure of colloidal state polymer, the two mixes initiated polymerization and forms colloidal state polymer by acrylate monomers and initiator, or mixes initiated polymerization by acrylate, linking agent and initiator three and form;
A, colloidal state polymer electrolyte precursor liquid solution are the mixing solutions of polymer monomer and electrolyte solution, or the mixing solutions of polymer monomer, linking agent and electrolyte solution, wherein:
Polymer monomer is an acrylate: its structure is CH
2=C (R
1) COOM, wherein R
1The structure of group is H or CH
3, M is H
+Or NH
4 +, basic metal or alkaline-earth metal, the overall mass fraction of shared mixing solutions is 5～50wt%;
When linking agent, linking agent is acrylamide and/or N, N '-methylene-bisacrylamide, and the overall mass fraction of shared mixing solutions is greater than 0～1.0wt%;
Electrolyte solution can be one of basic solution, acidic solution or neutral solution, and concentration is 1～10mol/L, and the overall mass fraction of shared mixing solutions is 50～95wt%;
B, the initiator that is used for initiated polymerization are polyreaction initiators commonly used, can be a kind of of hydrogen peroxide, persulphate, persulphate and sulphite or thiosulphate, and its consumption umber is 0.01～1.0wt% of mixing solutions oeverall quality;
The summation of each component is 100wt%.
2, colloidal state polymer ionogen as claimed in claim 1 is characterized in that described basic metal is K
+Or Na
+Or Li
+, alkaline-earth metal is Mg or Ca or Ba ion.
3, colloidal state polymer ionogen as claimed in claim 1 is characterized in that described basic solution can be KOH, NaOH, LiOH, Ba (OH)
2One of; Acidic solution can be HCl, HNO
3, H
2SO
4One of; Neutral solution can be NaCl, KCl, MgCl
2One of.
4, colloidal state polymer electrolyte preparation method as claimed in claim 1, it is characterized in that with acrylate monomers and the two mixing of electrolyte solution or acrylate monomers, electrolyte solution and linking agent three mixing, make the precursor solution of homogeneous, stable, modest viscosity, add initiator then, make monomer generation chemical crosslink reaction, form polymer network structure, liquid electrolyte is fixed in the microstructure of polymer network, thereby obtains the colloidal polymer dielectric.
5, colloidal state polymer electrolyte preparation method as claimed in claim 4 is characterized in that described basic metal is K
+Or Na
+Or Li
+, alkaline-earth metal is Mg or Ca or Ba ion.
6, colloidal state polymer electrolyte preparation method as claimed in claim 4 is characterized in that described basic solution can be KOH, NaOH, LiOH, Ba (OH)
2One of; Acidic solution can be HCl, HNO
3, H
2SO
4One of; Neutral solution can be NaCl, KCl, MgCl
2One of.
7, colloidal state polymer electrolyte preparation method as claimed in claim 4 is characterized in that 10～80 ℃ of polymer monomer polymerization temperatures.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100607006A CN1296430C (en) | 2004-08-09 | 2004-08-09 | Colloidal polymer electrolyte and preparation process thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100607006A CN1296430C (en) | 2004-08-09 | 2004-08-09 | Colloidal polymer electrolyte and preparation process thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1597766A CN1597766A (en) | 2005-03-23 |
| CN1296430C true CN1296430C (en) | 2007-01-24 |
Family
ID=34666316
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2004100607006A Expired - Fee Related CN1296430C (en) | 2004-08-09 | 2004-08-09 | Colloidal polymer electrolyte and preparation process thereof |
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|---|---|
| CN (1) | CN1296430C (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100424926C (en) * | 2005-11-10 | 2008-10-08 | 财团法人工业技术研究院 | High ion conductivity colloid polyelectrolyte for chargeable and dischargeable polymer secondary battery |
| CN110212137A (en) * | 2019-05-29 | 2019-09-06 | 常州优特科新能源科技有限公司 | A kind of preparation method and application of zinc system alkaline battery diaphragm |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1317512A (en) * | 2001-05-25 | 2001-10-17 | 复旦大学 | Process for preparing gel-state lithium ion polymer as electrolyte and bettery |
| CN1340219A (en) * | 1999-02-17 | 2002-03-13 | 三洋化成工业株式会社 | Gelating agent for alkaline cell and alkaline cell |
-
2004
- 2004-08-09 CN CNB2004100607006A patent/CN1296430C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1340219A (en) * | 1999-02-17 | 2002-03-13 | 三洋化成工业株式会社 | Gelating agent for alkaline cell and alkaline cell |
| CN1317512A (en) * | 2001-05-25 | 2001-10-17 | 复旦大学 | Process for preparing gel-state lithium ion polymer as electrolyte and bettery |
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| Publication number | Publication date |
|---|---|
| CN1597766A (en) | 2005-03-23 |
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