CN104953068A - Nanometer chitosan composite diaphragm of lithium battery and manufacturing method of nanometer chitosan composite diaphragm - Google Patents
Nanometer chitosan composite diaphragm of lithium battery and manufacturing method of nanometer chitosan composite diaphragm Download PDFInfo
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- CN104953068A CN104953068A CN201410111400.XA CN201410111400A CN104953068A CN 104953068 A CN104953068 A CN 104953068A CN 201410111400 A CN201410111400 A CN 201410111400A CN 104953068 A CN104953068 A CN 104953068A
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- nano chitosan
- lithium battery
- chitosan composite
- composite lithium
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/20—Manufacture of shaped structures of ion-exchange resins
- C08J5/22—Films, membranes or diaphragms
- C08J5/2206—Films, membranes or diaphragms based on organic and/or inorganic macromolecular compounds
- C08J5/2212—Natural macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/0427—Coating with only one layer of a composition containing a polymer binder
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2405/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2401/00 or C08J2403/00
- C08J2405/08—Chitin; Chondroitin sulfate; Hyaluronic acid; Derivatives thereof
-
- 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 belongs to the field of manufacturing of lithium batteries, and relates to a nanometer chitosan composite diaphragm of a lithium battery and a manufacturing method of the nanometer chitosan composite diaphragm. An ionic polymer membrane material composed of a (nanometer chitosan sol particles and micrometer chitosan sol particles) network and olefin copolymerized latex/polyethylene oxide is provided. According to the ionic polymer membrane material, the (nanometer chitosan sol particles and micrometer chitosan sol particles) network is adopted as a support body, and the nanometer chitosan composite diaphragm is formed through curtain coating and drying. The diaphragm has excellent three-dimensional network conformation, the porosity is 80% or more, and the thickness of the diaphragm is 5-60 micrometers. The diaphragm has no stress effect or form memory effect, has good chemical stability, form dimensional stability, thermal stability, insulativity and excellent physical mechanical strength (including tension resistance, impact resistance and flexibility in bending and the like), and has good adsorption affinity with an electrolyte. The nanometer chitosan composite diaphragm has positive charge characteristics, and can provide a free channel for positive electric lithium ions.
Description
Technical field
The invention belongs to lithium battery manufacturing technology field, relate to a kind of Nano chitosan composite lithium battery membrane and manufacture method thereof.
Background technology
Barrier film is one of important composition component of lithium battery, and its microcellular structure, physical property, chemical characteristic, hot property etc. are closely related with lithium battery performance.It is high that lithium battery has operating voltage, the positive and negative pole material of lithium battery diaphragm material and high electrochemical activity, should possess excellent compatibility; And as battery diaphragm material, excellent stability, solvent resistance, ionic conductivity, electrical insulating property, thermal endurance and good physical and mechanical properties (anti-tensile, shock resistance, pliable and toughly to circumnutate) also should be possessed.
Now, the PP/PE class material dominating material as lithium battery diaphragm is fissure type micropore (gap), porosity low (being generally 40-50%), and its imbibition is limited with guarantor's liquid space.
PP/PE class is non-polar material, and between polar electrolyte, affinity is poor, affects its imbibition and liquid-keeping property further.And diaphragm material micropore spy card and and polar electrolyte between compatibility, closely related with battery charging/discharging service life cycle;
Due to the diaphragm material imbibition of PP/PE class and liquid-keeping property low, its interface resistance is comparatively large, causes ionic conductivity not high, directly affects lithium battery performance.
Due to the hot shaping of PP/PE material, therefore PP/PE material fissure type micropore (gap) thermally-stabilised difference.
Because PP/PE class diaphragm material is physical extension pore (gap) or solvent extraction pore, this type of hole exists:
1. diaphragm material more or less residual mechanical stress effect.
2., after such membrane material is heated, the memory effect of the original form of restorer is had, and the mistake effect of holes of the larger contraction of generation/cause the high heat of diaphragm material blocking effect (function) forfeiture/electric pole short circuit/generation to positive/negative and burn, explode!
Summary of the invention
Technological innovation characteristics of the present invention is, utilize in following Chinese invention patent (patent No.: ZL02113792.6) claim 4, the end product (Nano chitosan colloidal sol) that B material (micron shitosan colloidal sol) of second step synthesis and Chinese invention patent (patent No.: ZL200410081608.8) synthesize, there is provided a kind of Nano chitosan colloidal sol/micron shitosan sol particles network of tool three-dimensional conformation as timbering material, load with/in conjunction with olefinic copolymer latex/poly(ethylene oxide), the ionomer membrane material of formation.It makes supporter with (Nano chitosan sol particles and micron shitosan sol particles) network, through curtain coating, drying, forms Nano chitosan composite lithium battery membrane.The excellent three dimensional network conformation of this film tool, excellent resistance to thermal dimensional stability, splendid electrolyte compatibility, ionic conductivity, electrical insulating property and good physical and mechanical properties (anti-tensile, shock resistance, pliable and toughly to circumnutate).
The Nano chitosan composite lithium battery membrane of any specification, size can be obtained by the present invention program.This thickness is 5 ~ 60 μm.
The Nano chitosan composite lithium battery membrane prepared by the present invention program, production technology, equipment are thrown few, and product cost is lower than existing PP/PE class barrier film (PP/PE class separator product cost: 4 yuans/square metre).
The Nano chitosan composite lithium battery membrane that the present invention proposes, tool excellent film forming, high heat-resistant stability (weightless temperature: >=200 DEG C), without the physical mechanical strength excellent performance (anti-tensile, shock resistance, pliable and toughly to circumnutate) of hot shaping, film.
The Nano chitosan composite lithium battery membrane that the present invention proposes, acid and alkali resistance.
The Nano chitosan composite lithium battery membrane that the present invention proposes, in battery electrolyte and under-40-150 DEG C of conditions, chemical stability, electrochemical stability and physical mechanical stability that tool is excellent.
The Nano chitosan composite lithium battery membrane that the present invention proposes, the insulating properties of tool excellence, will effectively stop the flowing of electronics and prevent the short circuit of lithium battery positive and negative electrode.Can be combination and the battery of battery lead plate, more Large Copacity, higher electromotive force are provided.
The Nano chitosan composite lithium battery membrane that the present invention proposes, tool ecosystem three-dimensional network conformation and positive electricity feature thereof, the splendid lithium ion permeability of tool is (outside under current field condition, more favourable positive electricity lithium ion passes through smoothly from Nano chitosan film three-dimensional mesh), can in lithium battery charge/discharge process, for combination and the battery of battery lead plate, provide more Large Copacity, higher electromotive force.
The Nano chitosan composite lithium battery membrane that the present invention proposes, tool ecosystem three-dimensional network conformation, unstressed effect, without form memory effect.
The Nano chitosan composite lithium battery membrane that the present invention proposes, the insulating properties of tool excellence, with the good affinity of electrolyte and hydrophily.
The Nano chitosan composite lithium battery membrane that the present invention proposes, porosity is greater than 80% (PP/PE class barrier film is 40-50%), with electrolyte tool good affinity and hydrophily.Tortuosity, imbibition/guarantor's liquid function that tool is more excellent and the electronic isolation of swellable and increase ionic conduction after this film Electolyte-absorptive.
The above-mentioned characteristic of Nano chitosan film, will effectively improve the combination property of lithium battery.
Accompanying drawing explanation
Fig. 1,2 be Nano chitosan composite lithium battery membrane of the present invention videotape microphoto (× 900 times)
Mode below by way of concrete embodiment does further statement to the present invention, but does not represent the present invention and can only implement in the following manner.
Embodiment
Technological innovation characteristics of the present invention is, utilize in following Chinese invention patent (patent No.: ZL02113792.6) claim 4, the end product (Nano chitosan colloidal sol) that B material (micron shitosan colloidal sol) of second step synthesis and Chinese invention patent (patent No.: ZL200410081608.8) synthesize, there is provided (Nano chitosan sol particles/micron shitosan sol particles) network of a kind of tool three-dimensional conformation as timbering material, load with/in conjunction with olefinic copolymer latex/poly(ethylene oxide), form Nano chitosan/composite lithium battery membrane glue, through curtain coating, dry, form Nano chitosan composite lithium battery membrane.The excellent three dimensional network conformation of this film tool, excellent resistance to thermal dimensional stability, splendid electrolyte compatibility, ionic conductivity, electrical insulating property and good physical and mechanical properties (anti-tensile, shock resistance, pliable and toughly to circumnutate).
As preferred version of the present invention, the thickness of Nano chitosan composite lithium battery membrane is 5 ~ 60 μm.
Nano chitosan composite lithium battery membrane provided by the invention is prepared from by following methods:
1., by amount of calculation poly(ethylene oxide) and amount of calculation deionized water, Forced Dispersion 30 minutes in strong dispersion pond and under room temperature, making the poly(ethylene oxide) aqueous solution is A material, for subsequent use.
2. utilize in following Chinese invention patent (patent No.: ZL 02113792.6) claim 4 by amount of calculation, compound prepared by the end product (Nano chitosan colloidal sol) that B material (micron shitosan colloidal sol) of second step synthesis and Chinese invention patent (patent No.: ZL200410081608.8) synthesize, for B material, for subsequent use.
3. the B of amount of calculation material being placed in reactor, under at room temperature with 500 revs/min of Forced Dispersion conditions, A material being directly added on B and expecting in reactor, after A material adds, keep 20 minutes again with under condition, is C material.
4. under the C of amount of calculation expects at room temperature with 500 revs/min of Forced Dispersion conditions, by the charging rate of 20 gram/minute, progressively the olefinic copolymer latex (commercial goods) of amount of calculation being added to C expects in still, after the olefinic copolymer latex of waiing upon amount of calculation has added, keep 1 hour again with under condition, obtain Nano chitosan composite lithium battery membrane glue product.
4. by Nano chitosan composite lithium battery membrane glue, through salivation, be uniformly distributed on a pet film, drying (25 ~ 35 DEG C), form Nano chitosan composite lithium battery membrane, this thickness is 5 ~ 60 μm.
As preferred version of the present invention, poly(ethylene oxide) aqueous solution ratio is 100 parts of weight deionized waters, adds poly(ethylene oxide) butt material 1.0 parts of weight.
As preferred version of the present invention, the parts by weight proportioning of micron shitosan colloidal sol and Nano chitosan colloidal sol is 6: 4.
As preferred version of the present invention, the parts by weight proportioning of (micron shitosan colloidal sol and Nano chitosan colloidal sol) compound butt and poly(ethylene oxide) is 6: 1.5.
As preferred version of the present invention, the parts by weight proportioning of (micron shitosan colloidal sol and Nano chitosan colloidal sol) compound butt and olefinic copolymer latex butt (commercial goods) is 1: 1.
Embodiment 1
1., by 1.5 grams of polyethylene oxide resins and 100 grams of deionized waters, Forced Dispersion 30 minutes in strong dispersion pond and under room temperature, making the poly(ethylene oxide) aqueous solution is A material, for subsequent use.
2. by 120 grams utilize in following Chinese invention patent (patent No.: ZL 02113792.6) claim 4, compound prepared by the end product (Nano chitosan colloidal sol) that B material (micron shitosan colloidal sol) of second step synthesis and 80 grams of Chinese invention patents (patent No.: ZL 200410081608.8) are synthesized, for B material, for subsequent use.
3. the B of 200 grams material being placed in reactor, under at room temperature with 500 revs/min of Forced Dispersion conditions, 10 grams of A material being directly added on B and expecting in reactor, after A material adds, keep 20 minutes again with under condition, is C material.
4. under the C of 205 grams being expected at room temperature with 500 revs/min of Forced Dispersion conditions, by the charging rate of 20 gram/minute, progressively the styrene-acrylic latex (commercial goods) of 30 grams being added to C expects in still, wait upon after styrene-acrylic latex (commercial goods) added, keep 1 hour again with under condition, obtain Nano chitosan composite lithium battery membrane glue product.
5. by Nano chitosan composite lithium battery membrane glue, through salivation, be uniformly distributed on a pet film, drying (25 ~ 35 DEG C), form Nano chitosan composite lithium battery membrane, this thickness is 5 ~ 60 μm.
Embodiment 2
1., by 2.5 grams of polyethylene oxide resins and 100 grams of deionized waters, Forced Dispersion 30 minutes in strong dispersion pond and under room temperature, making the poly(ethylene oxide) aqueous solution is A material, for subsequent use.
2. by 100 grams utilize in following Chinese invention patent (patent No.: ZL02113792.6) claim 4, compound prepared by the end product (Nano chitosan colloidal sol) that B material (micron shitosan colloidal sol) of second step synthesis and 100 grams of Chinese invention patents (patent No.: ZL200410081608.8) are synthesized, for B material, for subsequent use.
3. the B of 215 grams material being placed in reactor, under at room temperature with 500 revs/min of Forced Dispersion conditions, 30 grams of A material being directly added on B and expecting in reactor, after A material adds, keep 20 minutes again with under condition, is C material.
4. under the C of 245 grams being expected at room temperature with 500 revs/min of Forced Dispersion conditions, by the charging rate of 20 gram/minute, progressively the styrene-butadiene latex (commercial goods) of 15 grams being added to C expects in still, wait upon after styrene-butadiene latex added, keep 1 hour again with under condition, obtain Nano chitosan composite lithium battery membrane glue product.
5. by Nano chitosan composite lithium battery membrane glue, through salivation, be uniformly distributed on a pet film, drying (25 ~ 35 DEG C), form Nano chitosan composite lithium battery membrane, this thickness is 5 ~ 60 μm.
Embodiment 3
1., by 1.0 grams of polyethylene oxide resins and 100 grams of deionized waters, Forced Dispersion 30 minutes in strong dispersion pond and under room temperature, making the poly(ethylene oxide) aqueous solution is A material, for subsequent use.
2. by 40 grams utilize in following Chinese invention patent (patent No.: ZL02113792.6) claim 4, compound prepared by the end product (Nano chitosan colloidal sol) that B material (micron shitosan colloidal sol) of second step synthesis and 160 grams of Chinese invention patents (patent No.: ZL200410081608.8) are synthesized, for B material, for subsequent use.
3. the B of 200 grams material being placed in reactor, under at room temperature with 500 revs/min of Forced Dispersion conditions, 30 grams of A material being directly added on B and expecting in reactor, after A material adds, keep 20 minutes again with under condition, is C material.
4. under the C of 230 grams being expected at room temperature with 500 revs/min of Forced Dispersion conditions, by the charging rate of 20 gram/minute, progressively the NBR latex (40% solid content commercial goods) of 10 grams being added to C expects in still, wait upon after NBR latex added, keep 1 hour again with under condition, obtain Nano chitosan composite lithium battery membrane glue product.
5. by Nano chitosan composite lithium battery membrane glue, through salivation, be uniformly distributed on a pet film, drying (25 ~ 35 DEG C), form Nano chitosan composite lithium battery membrane, this thickness is 5 ~ 60 μm.
Claims (5)
1. a Nano chitosan composite lithium battery membrane and manufacture method, utilize in following Chinese invention patent (patent No.: ZL02113792.6) claim 4, the end product (Nano chitosan colloidal sol) that B material (micron shitosan colloidal sol) of second step synthesis and Chinese invention patent (patent No.: ZL200410081608.8) synthesize, there is provided a kind of Nano chitosan colloidal sol/micron shitosan sol particles network of tool three-dimensional conformation as timbering material, load with/in conjunction with olefines copolymer latex/poly(ethylene oxide), the ionomer membrane material formed.It makes supporter with (Nano chitosan sol particles and micron shitosan sol particles) network, on a pet film through curtain coating, drying, forms Nano chitosan composite lithium battery membrane.The excellent three dimensional network conformation of this film tool, excellent resistance to thermal dimensional stability, splendid electrolyte compatibility, ionic conductivity, electrical insulating property and good physical and mechanical properties (anti-tensile, shock resistance, pliable and toughly to circumnutate).
2. it is 5 ~ 60 μm by the thickness of a kind of Nano chitosan composite lithium battery membrane according to claim 1.
3. be prepared from by following methods by a kind of Nano chitosan composite lithium battery membrane according to claim 1:
1. by the polyethylene oxide resin (weight average molecular mass: the commercial goods of 4,000,000) of 1.0-2.5 parts by weight and the deionized water of 100 parts by weight, Forced Dispersion 30 minutes in strong dispersion pond and under room temperature, making the poly(ethylene oxide) aqueous solution is A material, for subsequent use.
2. utilize in following Chinese invention patent (patent No.: ZL02113792.6) claim 4 by 40--120 parts by weight, compound prepared by the end product (Nano chitosan colloidal sol) that B material (micron shitosan colloidal sol) of second step synthesis and the Chinese invention patent (patent No.: ZL200410081608.8) of 80--160 parts by weight synthesize, be B material under at room temperature with 500 revs/min of Forced Dispersion conditions, for subsequent use.
3. the B of 200--215 parts by weight material being placed in reactor, under at room temperature with 500 revs/min of Forced Dispersion conditions, being expected by the A of 10--30 parts by weight, be directly added on B and expect in reactor, after A material adds, keep 20 minutes again with under condition, is C material.
4. under the C of 210--245 parts by weight expects at room temperature with 500 revs/min of Forced Dispersion conditions, by the charging rate of 20 gram/minute, progressively the styrene-butadiene latex (40% solid content commercial goods) of 10--30 parts by weight being added to C expects in still, wait upon after styrene-butadiene latex added, keep 1 hour again with under condition, obtain Nano chitosan composite lithium battery membrane glue product.
4. by Nano chitosan composite lithium battery membrane according to claim 3, it is the Nano chitosan composite lithium battery membrane glue product that will obtain, through salivation, be uniformly distributed on a pet film with dry (25 ~ 35 DEG C), form Nano chitosan composite lithium battery membrane, this thickness is 5 ~ 60 μm.
5. by Nano chitosan composite lithium battery membrane according to claim 3, poly(ethylene oxide) aqueous solution ratio is 100 parts of weight deionized waters, adds poly(ethylene oxide) butt material 1.0-2.5 parts of weight.Polyethylene oxide resin is weight average molecular mass: the commercial goods of 4,000,000.
7. by Nano chitosan composite lithium battery membrane according to claim 3, the parts by weight proportioning of its micron of shitosan colloidal sol and Nano chitosan colloidal sol is 0.25/1.0 ~ 1.5/1.0.
8. by Nano chitosan composite lithium battery membrane according to claim 3, the parts by weight proportioning of its (micron shitosan colloidal sol and Nano chitosan colloidal sol) compound butt and poly(ethylene oxide) butt is 6.0/0.1 ~ 6.0/0.3.
9. by Nano chitosan composite lithium battery membrane according to claim 3, micron shitosan colloidal sol and Nano chitosan colloidal sol) the parts by weight proportioning of compound butt and styrene-butadiene latex butt (commercial goods) is 1/1 ~ 1/2.
10. by olefines copolymer latex according to claim 1 be: commercial goods styrene-butadiene latex, NBR latex, styrene-acrylic latex etc.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410111400.XA CN104953068A (en) | 2014-03-25 | 2014-03-25 | Nanometer chitosan composite diaphragm of lithium battery and manufacturing method of nanometer chitosan composite diaphragm |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201410111400.XA CN104953068A (en) | 2014-03-25 | 2014-03-25 | Nanometer chitosan composite diaphragm of lithium battery and manufacturing method of nanometer chitosan composite diaphragm |
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| CN104953068A true CN104953068A (en) | 2015-09-30 |
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| CN201410111400.XA Pending CN104953068A (en) | 2014-03-25 | 2014-03-25 | Nanometer chitosan composite diaphragm of lithium battery and manufacturing method of nanometer chitosan composite diaphragm |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109244328A (en) * | 2018-09-25 | 2019-01-18 | 合肥先杰新能源科技有限公司 | Lithium ion battery separator and preparation method thereof |
| CN109920954A (en) * | 2019-03-14 | 2019-06-21 | 王在福 | A kind of Nano chitosan composite lithium battery membrane and its manufacturing method |
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| CN109920954A (en) * | 2019-03-14 | 2019-06-21 | 王在福 | A kind of Nano chitosan composite lithium battery membrane and its manufacturing method |
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Inventor after: Gong Zhenglie Inventor after: Wang Zaifu Inventor after: Gong Baohong Inventor before: Guo Xiaoping Inventor before: Sun Qingbin Inventor before: Gong Zhenglie Inventor before: Gong Baohong |
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Application publication date: 20150930 |