CN104953069A - Nanometer chitosan compound/fiber composite diaphragm for lithium battery and preparation method of diaphragm - Google Patents
Nanometer chitosan compound/fiber composite diaphragm for lithium battery and preparation method of diaphragm Download PDFInfo
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- CN104953069A CN104953069A CN201410111429.8A CN201410111429A CN104953069A CN 104953069 A CN104953069 A CN 104953069A CN 201410111429 A CN201410111429 A CN 201410111429A CN 104953069 A CN104953069 A CN 104953069A
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- fiber
- compound
- nano chitosan
- lithium battery
- chitosan compound
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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
- H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
-
- 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
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Cell Separators (AREA)
Abstract
The invention belongs to the field of manufacturing of lithium batteries, and in particular relates to a nanometer chitosan compound/fiber composite diaphragm for a lithium battery and a preparation method of the diaphragm. According to the invention, an ionic polymer membrane material is formed by loading and combining of nanometer chitosan compound particles and natural non-woven fiber; the natural non-woven fiber is adopted as a support, and the nanometer chitosan compound/fiber composite diaphragm is obtained through rolling and drying (at 40-50 EG C), wherein the thickness of the nanometer chitosan compound/fiber composite diaphragm is 5-60 micrometers. The nanometer chitosan compound/fiber composite diaphragm has excellent three-dimensional network conformation, and the porosity is 80% or above; the nanometer chitosan compound/fiber composite diaphragm has no stress effect or form memory effect. The nanometer chitosan compound/fiber composite diaphragm has chemical stability, form dimensional stability, thermal stability, insulativity and excellent physical mechanical strength: fracture length(Km):4.3, and annular pressure index (kgf/152mm/Nm/g):11.92 in electrolyte and under -40 DEG C to 150 DEG C, and has excellent adsorption affinity with the electrolyte. The nanometer chitosan compound/fiber 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 the compound (being called for short: Nano chitosan compound)/natural nonwoven fiber (being called for short: fiber) that a kind of Nano chitosan particle and micron chitosan particles form and combine lithium battery diaphragm 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 character 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-up feature (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 composite sol particles and aqueous dispersion natural fiber of tool three-dimensional network conformation, the Nano chitosan compound through loading with, being bonded/fiber combinations lithium battery diaphragm material.This Nano chitosan composite/fiber combinations material makes supporter with natural nonwoven fiber, through exhibition pressure, dry formation Nano chitosan compound/fiber combinations book film.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).
Nano chitosan compound/fiber combinations the lithium battery diaphragm of any specification, size can be obtained by the present invention program.Membrane thicknesses 5-60 μm.
Nano chitosan compound/fiber combinations the lithium battery diaphragm prepared by the present invention program, production technology is easy, equipment investment is few, and product cost is lower than existing PP/PE class barrier film (PP/PE class separator product cost: 4 yuans/square metre).
Nano chitosan compound/fiber combinations lithium battery diaphragm film that the present invention proposes, tool excellent film forming, high heat-resistant stability (weightless temperature: >=+256 DEG C), without the physical mechanical strength function admirable " fracture length (Km): 4.3, ring crush index (kgf/152mm/Nm/g): 11.92 " of hot shaping, film.
Nano chitosan compound/fiber combinations lithium battery diaphragm that the present invention proposes, acid and alkali resistance.
Nano chitosan compound/fiber combinations lithium battery diaphragm 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.
Nano chitosan compound/fiber combinations lithium battery diaphragm that the present invention proposes, the insulating properties that tool is excellent, 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.
Nano chitosan compound/fiber combinations lithium battery diaphragm 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 in 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.
Nano chitosan compound/fiber combinations lithium battery diaphragm that the present invention proposes, porosity is greater than 80% (PP/PE class barrier film is 40-50%), imbibition/guarantor's liquid function that tool is more excellent, and its interface resistance is less and ionic conductivity is higher.
Nano chitosan compound/fiber combinations lithium battery diaphragm that the present invention proposes, tool ecosystem three-dimensional network conformation, unstressed effect, without form memory effect.
Nano chitosan compound/fiber combinations lithium battery diaphragm that the present invention proposes, the insulating properties of tool excellence, with the good affinity of electrolyte and hydrophily.The above-mentioned characteristic of Nano chitosan saccharide complex/fiber combinations lithium battery diaphragm, will effectively improve the combination property of lithium battery.
Accompanying drawing explanation
To be the present invention videotape microphoto (× 3900 times) as the blank natural nonwoven fiber of Nano chitosan particle and micron chitosan particles supporter to Fig. 1,2.
Fig. 3,4 be Nano chitosan of the present invention compound/fiber combinations lithium battery diaphragm videotape microphoto (× 3900 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
The invention provides a kind of Nano chitosan compound/fiber combinations pond diaphragm material, 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 compound and aqueous dispersion natural fiber of tool three-dimensional network conformation, the Nano chitosan compound through loading with, being bonded/fiber combinations pond diaphragm material.This Nano chitosan compound/fiber combinations pond diaphragm material makes supporter with natural nonwoven fiber, through loading with, combining, open up pressure, dry (40 ~ 50 DEG C), forms nanometer chitosan fiber combination book film.
As preferred version of the present invention, the thickness of Nano chitosan compound/fiber combinations lithium battery diaphragm is 5 ~ 60 μm.
Nano chitosan compound/fiber combinations lithium battery diaphragm provided by the invention is prepared from by following methods:
1. by amount of calculation Native fibril and amount of calculation deionized water, Forced Dispersion 30 minutes in strong dispersion pond and under room temperature, then be placed in 35 ~ 40 DEG C of container Forced Dispersions 1 hour, be placed in Special dispersing groove as aqueous dispersion fiber base-material.
2. utilize in following Chinese invention patent (patent No.: ZL02113792.6) 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, directly/disposable to entering in aqueous dispersion natural nonwoven fiber base hopper, after natural nonwoven fiber dispersion is even, breakdown aqueous dispersion fiber base hopper lower end valve, drain disperse water in natural nonwoven fiber base hopper fast, load with, in conjunction with the natural fiber of micron chitosan particles and Nano chitosan particle, uniform deposition is on screen cloth.Nano chitosan compound/fiber combinations material, through exhibition pressure, dry (40 ~ 50 DEG C), form nanometer chitosan fiber combination book film, this thickness is 5 ~ 60 μm.
As preferred version of the present invention, the ratio of aqueous dispersion fiber is 100 parts by weight deionized waters, adds dry fiber base-material 0.38 parts by weight.
As preferred version of the present invention, the proportioning of micron shitosan colloidal sol and Nano chitosan colloidal sol is 3/2 parts by weight.
As preferred version of the present invention, the proportioning of (micron shitosan colloidal sol and Nano chitosan colloidal sol) compound butt and dry fiber base-material is 4: 5 parts by weight.
Embodiment 1
1. by 1.52 grams of Native fibril and 400 grams of deionized waters, Forced Dispersion 30 minutes in strong dispersion pond and under room temperature, then be placed in 35 ~ 40 DEG C of container Forced Dispersions 1 hour, be placed in Special dispersing groove as aqueous dispersion fiber base-material.
2. 5 grams are utilized in following Chinese invention patent (patent No.: ZL02113792.6) claim 4, compound (micron shitosan colloidal sol: Nano chitosan colloidal sol/3 gram: 2 grams) 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, directly/and disposable to entering in aqueous dispersion fiber base hopper, gently stir.After fiber dispersion is even, breakdown aqueous dispersion fiber base hopper lower end valve, drain disperse water in fiber base hopper fast, load with, combine the natural fiber of micron chitosan particles and Nano chitosan particle, uniform deposition is on screen cloth.Nano chitosan compound/fiber combinations material, through exhibition pressure, dry (40 ~ 50 DEG C), form nanometer chitosan fiber combination book film, this thickness is 5 ~ 60 μm.
Embodiment 2
1. by 1.52 grams of Native fibril and 400 grams of deionized waters, Forced Dispersion 30 minutes in strong dispersion pond and under room temperature, then be placed in 35 ~ 40 DEG C of container Forced Dispersions 1 hour, be placed in Special dispersing groove as aqueous dispersion fiber base-material.
2. 10 grams are utilized in following Chinese invention patent (patent No.: ZL02113792.6) claim 4, compound (micron shitosan colloidal sol: Nano chitosan colloidal sol/5 gram: 5 grams) 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, directly/and disposable to entering in aqueous dispersion fiber base hopper, gently stir.After fiber dispersion is even, breakdown aqueous dispersion fiber base hopper lower end valve, drain disperse water in fiber base hopper fast, load with, combine the natural fiber of micron chitosan particles and Nano chitosan particle, uniform deposition is on screen cloth.Nano chitosan compound/fiber combinations material, through exhibition pressure, dry (40 ~ 50 DEG C), form nanometer chitosan fiber combination book film, this thickness is 5 ~ 60 μm.
Embodiment 3
1. by 1.52 grams of Native fibril and 400 grams of deionized waters, Forced Dispersion 30 minutes in strong dispersion pond and under room temperature, then be placed in 35 ~ 40 DEG C of container Forced Dispersions 1 hour, be placed in Special dispersing groove as aqueous dispersion fiber base-material.
2. 8 grams are utilized in following Chinese invention patent (patent No.: ZL02113792.6) claim 4, compound (micron shitosan colloidal sol: Nano chitosan colloidal sol/6 gram: 2 grams) 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, directly/and disposable to entering in aqueous dispersion fiber base hopper, gently stir.After fiber dispersion is even, breakdown aqueous dispersion fiber base hopper lower end valve, drain disperse water in fiber base hopper fast, load with, combine the natural fiber of micron chitosan particles and Nano chitosan particle, uniform deposition is on screen cloth.Nano chitosan compound/fiber combinations material, through exhibition pressure, dry (40 ~ 50 DEG C), form nanometer chitosan fiber combination book film, this thickness is 5 ~ 60 μm.
Claims (6)
1. the compound be made up of Nano chitosan particle and micron chitosan particles (being called for short: Nano chitosan compound)/fiber combinations lithium battery diaphragm and manufacture method thereof, 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, a kind of Nano chitosan compound sol particles and aqueous dispersion natural nonwoven fiber (being called for short: fiber) of tool three-dimensional network conformation are provided, through loading with, the Nano chitosan compound be bonded/fiber combinations lithium battery diaphragm material.This Nano chitosan compound/fiber combinations lithium battery diaphragm makes supporter with fiber, through loading with, combining, open up pressure, dry (40 ~ 50 DEG C), forms nanometer chitosan fiber combination book film.
2. it is 5 ~ 60 μm by the thickness of a kind of Nano chitosan compound/fiber combinations lithium battery diaphragm according to claim 1.
3. be prepared from by following methods by a kind of Nano chitosan compound/fiber combinations lithium battery diaphragm according to claim 1:
1. by the Native fibril of 1 ~ 10 parts by weight and 400 ~ 800 parts by weight deionized waters, Forced Dispersion 30 minutes in strong dispersion pond and under room temperature, be placed in 20 ~ 40 DEG C of container Forced Dispersions again 1 hour, be placed in Special dispersing groove as aqueous dispersion fiber base-material.
2. 2 ~ 20 parts by weight are utilized 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 Chinese invention patent (patent No.: ZL200410081608.8) synthesize, directly/disposable to entering in aqueous dispersion fiber base hopper, after fiber dispersion is even, breakdown aqueous dispersion fiber base hopper lower end valve, drain disperse water in fiber base hopper fast, load with, in conjunction with the natural fiber of micron chitosan particles and Nano chitosan particle, uniform deposition is on screen cloth.Nano chitosan compound/fiber combinations material, through exhibition pressure, dry (40 ~ 50 DEG C), form nanometer chitosan fiber combination book film, this thickness is 5 ~ 60 μm.
4., by described in the requirement 1 of wooden fork profit, a kind of Nano chitosan compound/fiber combinations lithium battery diaphragm, the ratio of aqueous dispersion fiber is 100 ~ 500 parts by weight deionized waters, adds 0.1 ~ 2.0 parts by weight dry fiber base-materials.
5. by wooden fork profit requirement 1 described in, the proportioning of a kind of Nano chitosan compound/fiber combinations lithium battery diaphragm micron shitosan colloidal sol and Nano chitosan colloidal sol is 1/1 ~ 1/3 parts by weight.
6. by wooden fork profit requirement 1 described in, the proportioning of a kind of Nano chitosan compound/fiber combinations lithium battery diaphragm (micron shitosan colloidal sol and Nano chitosan colloidal sol) compound butt and dry fiber base-material is 1/10 ~ 1/5 parts by weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410111429.8A CN104953069A (en) | 2014-03-25 | 2014-03-25 | Nanometer chitosan compound/fiber composite diaphragm for lithium battery and preparation method of diaphragm |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201410111429.8A CN104953069A (en) | 2014-03-25 | 2014-03-25 | Nanometer chitosan compound/fiber composite diaphragm for lithium battery and preparation method of diaphragm |
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| CN104953069A true CN104953069A (en) | 2015-09-30 |
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| CN201410111429.8A Pending CN104953069A (en) | 2014-03-25 | 2014-03-25 | Nanometer chitosan compound/fiber composite diaphragm for lithium battery and preparation method of diaphragm |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109920954A (en) * | 2019-03-14 | 2019-06-21 | 王在福 | A kind of Nano chitosan composite lithium battery membrane and its manufacturing method |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5514378A (en) * | 1993-02-01 | 1996-05-07 | Massachusetts Institute Of Technology | Biocompatible polymer membranes and methods of preparation of three dimensional membrane structures |
| CN1208350C (en) * | 2002-09-23 | 2005-06-29 | 广汉恒宇新材料有限公司 | Preparation of nanometer-sized cation polysaccharide |
| JP2005255876A (en) * | 2004-03-12 | 2005-09-22 | Asahi Kasei Corp | Microporous membrane and its manufacturing method |
| CN1795935B (en) * | 2004-12-28 | 2010-09-29 | 广汉恒宇新材料有限公司 | Artificial skin prepared from Nano chitosan and preparing method |
-
2014
- 2014-03-25 CN CN201410111429.8A patent/CN104953069A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5514378A (en) * | 1993-02-01 | 1996-05-07 | Massachusetts Institute Of Technology | Biocompatible polymer membranes and methods of preparation of three dimensional membrane structures |
| CN1208350C (en) * | 2002-09-23 | 2005-06-29 | 广汉恒宇新材料有限公司 | Preparation of nanometer-sized cation polysaccharide |
| JP2005255876A (en) * | 2004-03-12 | 2005-09-22 | Asahi Kasei Corp | Microporous membrane and its manufacturing method |
| CN1795935B (en) * | 2004-12-28 | 2010-09-29 | 广汉恒宇新材料有限公司 | Artificial skin prepared from Nano chitosan and preparing method |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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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Application publication date: 20150930 |
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