CN109920954A - A kind of Nano chitosan composite lithium battery membrane and its manufacturing method - Google Patents
A kind of Nano chitosan composite lithium battery membrane and its manufacturing method Download PDFInfo
- Publication number
- CN109920954A CN109920954A CN201910194235.1A CN201910194235A CN109920954A CN 109920954 A CN109920954 A CN 109920954A CN 201910194235 A CN201910194235 A CN 201910194235A CN 109920954 A CN109920954 A CN 109920954A
- Authority
- CN
- China
- Prior art keywords
- lithium battery
- nano chitosan
- composite lithium
- nano
- battery membrane
- 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.)
- Pending
Links
- 229920001661 Chitosan Polymers 0.000 title claims abstract description 105
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 67
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 67
- 239000012528 membrane Substances 0.000 title claims abstract description 56
- 239000002131 composite material Substances 0.000 title claims abstract description 50
- 238000004519 manufacturing process Methods 0.000 title abstract description 8
- 239000000463 material Substances 0.000 claims abstract description 67
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims abstract description 20
- 239000004816 latex Substances 0.000 claims abstract description 17
- 229920000126 latex Polymers 0.000 claims abstract description 17
- 239000000203 mixture Substances 0.000 claims abstract description 14
- 229920001577 copolymer Polymers 0.000 claims abstract description 12
- 239000002245 particle Substances 0.000 claims abstract description 8
- 229920000554 ionomer Polymers 0.000 claims abstract description 3
- 238000004364 calculation method Methods 0.000 claims description 21
- 239000006185 dispersion Substances 0.000 claims description 20
- 238000002360 preparation method Methods 0.000 claims description 15
- 239000003292 glue Substances 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 235000007164 Oryza sativa Nutrition 0.000 claims description 4
- 235000009566 rice Nutrition 0.000 claims description 4
- 239000002078 nanoshell Substances 0.000 claims description 2
- 241000209094 Oryza Species 0.000 claims 3
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims 1
- 239000003792 electrolyte Substances 0.000 abstract description 8
- 230000035939 shock Effects 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 abstract description 3
- 239000004698 Polyethylene Substances 0.000 description 11
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 9
- 230000005611 electricity Effects 0.000 description 9
- 229910001416 lithium ion Inorganic materials 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 239000007788 liquid Substances 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 238000005213 imbibition Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 230000006870 function Effects 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000003643 water by type Substances 0.000 description 4
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000009194 climbing Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 125000003367 polycyclic group Chemical group 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000002174 Styrene-butadiene Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 230000003446 memory effect Effects 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000007493 shaping process Methods 0.000 description 2
- 239000011115 styrene butadiene Substances 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- 229920001909 styrene-acrylic polymer Polymers 0.000 description 2
- 230000010148 water-pollination Effects 0.000 description 2
- 240000007594 Oryza sativa Species 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000000740 bleeding effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 125000005626 carbonium group Chemical group 0.000 description 1
- 210000005056 cell body Anatomy 0.000 description 1
- 230000001595 contractor effect Effects 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 208000021760 high fever Diseases 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000010220 ion permeability Effects 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
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 belongs to lithium battery manufacturing technology field, it is related to a kind of Nano chitosan composite lithium battery membrane and its manufacturing method.Olefinic copolymer latex/polyethylene oxide, the ionomer membrane material of composition are loaded with/combined to Nano chitosan composite lithium battery membrane to have the Nano chitosan of three-dimensional conformation colloidal sol/micron chitosan sol particle network as timbering material.It is to make supporter with Nano chitosan sol particles and micron chitosan sol particle network, is cast, is dried, and Nano chitosan composite lithium battery membrane is formed.The film has excellent three dimensional network conformation, excellent resistance to thermal dimensional stability, splendid electrolyte compatibility, ionic conductivity, electrical insulating property and good physical mechanical property (anti-tensile, flexible circumnutates at shock resistance).By the above-mentioned characteristic using Nano chitosan film provided by the invention, the comprehensive performance of lithium battery will be effectively improved.
Description
Technical field
The invention belongs to lithium battery manufacturing technology field, it is related to a kind of Nano chitosan composite lithium battery membrane and its manufacture
Method.
Background technique
Diaphragm is one of important composition component of lithium battery, its microcellular structure, physical property, chemical characteristic, hot property
Deng closely related with lithium battery performance.Lithium battery has operating voltage high, and lithium battery diaphragm material and high electrochemical activity are just
Negative electrode material should have excellent compatibility；And as battery diaphragm material, should also have excellent stability, solvent resistant
Property, ionic conductivity, electrical insulating property, heat resistance and good physical mechanical property (anti-tensile, flexible circumnutates at shock resistance).
Now, dominating the PP/PE class material of material as lithium battery diaphragm is crack type micro-hole (gap), and porosity is low
(generally 40-50%), imbibition and guarantor's liquid space are limited.
PP/PE class affinity between non-polar material, with polar electrolyte is poor, further influences its imbibition and protects liquid energy
Power.And the micropore spy card of diaphragm material and the compatibility between polar electrolyte, with the close phase of battery charging/discharging service life cycle
It closes；
Since PP/PE class diaphragm material imbibition and liquid-keeping property are low, interface resistance is larger, leads to ionic conductivity not
Height directly affects lithium battery performance.
Due to the hot shaping of PP/PE material, therefore PP/PE material crack type micro-hole (gap) thermostabilization is poor.
Since PP/PE class diaphragm material is physical extension pore (gap) or solvent extraction pore, such hole exists:
1. the more or less residual mechanical stress effect of diaphragm material.
2. having the memory effect of the original form of restorer after such membrane material is heated, and generate the mistake hole of larger contraction
Effect/cause diaphragm material to blocking effect (function) forfeiture/electric pole short circuit/generation high fever of positive/negative and burning, explosion！
Summary of the invention
Based on the above prior art, the purpose of the present invention is to provide a kind of Nano chitosan composite lithium battery membrane and its
Manufacturing method, to solve lithium battery diaphragm leading the problems such as material porosity is low, thermostabilization is poor to a certain extent.
In order to achieve the goal above, the technical solution adopted by the present invention are as follows:
A kind of Nano chitosan composite lithium battery membrane, with Nano chitosan colloidal sol/micron shell with three-dimensional conformation
Olefinic copolymer latex/polyethylene oxide, the ion of composition are loaded with/combined to glycan sol particles network as timbering material
Polymeric film material.
Further, the film thickness of the Nano chitosan composite lithium battery membrane is 5~60 μm, and porosity is greater than
80%.
Further, the Nano chitosan composite lithium battery membrane preparation method the following steps are included:
By calculation amount polyethylene oxide and calculation amount deionized water, in dispersion Chi Zhonghe by force, Forced Dispersion 30 divides at room temperature
Clock is made polyethylene oxide aqueous solution and expects for A, spare；
The micron chitosan sol of calculation amount and Nano chitosan colloidal sol are mixed and expected as B, it is spare；
The B material of calculation amount is placed in reaction kettle, at room temperature and under the conditions of 500 revs/min of Forced Dispersions, A is expected straight
It connects and is added in B material reaction kettle, after A material adds, keep 20 minutes under the conditions of, expect for C again；
The C of calculation amount expects at room temperature and under the conditions of 500 revs/min of Forced Dispersions, by the charging rate of 20 gram/minutes,
Gradually the olefinic copolymer latex of calculation amount is added in C material kettle, the olefinic copolymer latex for waiing upon calculation amount has added
Afterwards, it is kept again 1 hour under the conditions of, obtains Nano chitosan composite lithium battery membrane glue product；
It by Nano chitosan composite lithium battery membrane glue, is salivated, is uniformly distributed on a pet film, through drying, forms nanometer
Chitosan composite lithium battery membrane, the film thickness are 5~60 μm.
Further, the water-soluble liquid proportional of the polyethylene oxide is 100 parts by weight of deionized water, and 1.0 parts by weight of addition are poly-
Ethylene oxide butt material.
Further, the micron chitosan sol and the parts by weight of Nano chitosan colloidal sol proportion are 6: 4.
Further, the micron chitosan sol and the Nano chitosan colloidal sol mixture butt and the polycyclic oxygen
The parts by weight proportion of ethane is 6: 1.5.
Further, the micron chitosan sol and the Nano chitosan colloidal sol mixture butt and the olefines
The parts by weight proportion of copolymer emulsion butt is 1: 1.
Compared with prior art, the device have the advantages that it is as follows:
The present invention provides a kind of Nano chitosan colloidal sol/micron chitosan sol particle network of tool three-dimensional conformation as branch
Olefinic copolymer latex/polyethylene oxide, the ionomer membrane material of composition are loaded with/combined to frame material.It is with nanometer
Chitosan sol particle and micron chitosan sol particle network make supporter, are cast, are dried, and it is compound to form Nano chitosan
Lithium battery diaphragm.The film, which has excellent three dimensional network conformation, excellent resistance to thermal dimensional stability, splendid electrolyte compatibility, ion, leads
Electrically, electrical insulating property and good physical mechanical property (anti-tensile, flexible circumnutates at shock resistance).
Nano chitosan composite lithium battery membrane proposed by the present invention has excellent film forming, high heat-resistant stability (loses
Degree of reviewing: >=200 DEG C), no hot shaping, film physical mechanical strength have excellent performance that (anti-tensile, flexible circumnutates at shock resistance
Deng), and acid and alkali resistance in battery electrolyte and under the conditions of-40-150 DEG C, has excellent chemical stability, electrochemically stable
Property and physical mechanical stability.Further it is proposed that Nano chitosan composite lithium battery membrane, have excellent insulating properties,
By effective flowing for preventing electronics and the short circuit for preventing lithium battery positive and negative electrode, it can be combination and the battery of electrode plate, provide bigger
Capacity, higher electromotive force.Nano chitosan composite lithium battery membrane proposed by the present invention, have ecosystem three-dimensional network conformation and its
Positive electricity feature, having splendid lithium ion permeability, (under outer current field condition, more advantageous positive electricity lithium ion is from Nano chitosan film
Passed through in three-dimensional mesh), it can be combination and the battery of electrode plate, more great Rong is provided during lithium battery charge/discharge
Amount, higher electromotive force.Nano chitosan composite lithium battery membrane proposed by the present invention, has ecosystem three-dimensional network conformation, and nothing is answered
Stress effect, without form memory effect.Nano chitosan composite lithium battery membrane porosity proposed by the present invention is greater than 80% (PP/
PE class diaphragm is 40-50%), have good affinity and hydrophily, swellable and increase after the film Electolyte-absorptive with electrolyte
The tortuosity of ionic conduction has more preferably imbibition/guarantor's liquid function and electronic isolation.
In addition, the Nano chitosan composite lithium battery membrane of any specification, size can be obtained by the present invention program, and produce work
Skill, equipment are thrown less, and product cost is lower than existing PP/PE class diaphragm (PP/PE class separator product cost: 4 yuans/square
Rice).
To sum up, by the above-mentioned characteristic using Nano chitosan film provided by the invention, the comprehensive of lithium battery will be effectively improved
Close performance.
Detailed description of the invention
Fig. 1,2 are that Nano chitosan composite lithium battery membrane of the invention videotapes microphoto (× 900 times).
Specific embodiment
The nano spray plating liquid and spraying plating process for large-scale workpiece of the invention is made into one combined with specific embodiments below
Step is described in detail.
Nano chitosan composite lithium battery membrane provided by the invention is prepared by following methods:
1. in dispersion Chi Zhonghe by force, Forced Dispersion 30 divides at room temperature by calculation amount polyethylene oxide and calculation amount deionized water
Clock is made polyethylene oxide aqueous solution and expects for A, spare.
2. by calculation amount using in following Chinese invention patents (patent No.: ZL 02113792.6) claim 4,
The B material (micron chitosan sol) of two steps synthesis and the end of Chinese invention patent (patent No.: ZL200410081608.8) synthesis
The mixture of product (Nano chitosan colloidal sol) preparation is held, is expected for B, it is spare.
3. the B material of calculation amount is placed in reaction kettle, at room temperature and under the conditions of 500 revs/min of Forced Dispersions, A is expected
It is directly added in B material reaction kettle, after A material adds, keeps 20 minutes under the conditions of, expect for C again.
4. the C of calculation amount expects at room temperature and under the conditions of 500 revs/min of Forced Dispersions, by the charging speed of 20 gram/minutes
The olefinic copolymer latex (commercial goods) of calculation amount, is gradually added in C material kettle by degree, waits upon the olefines copolymerization of calculation amount
It after object latex has added, is kept again 1 hour under the conditions of, obtains Nano chitosan composite lithium battery membrane glue product.
4. Nano chitosan composite lithium battery membrane glue is salivated, it is uniformly distributed on a pet film, through drying (25~35
DEG C), Nano chitosan composite lithium battery membrane is formed, which is 5~60 μm.
As the preferred solution of the invention, the water-soluble liquid proportional of polyethylene oxide is 100 parts of weight deionized waters, adds polycyclic oxygen
1.0 parts of weight of ethane butt material.
As the preferred solution of the invention, the parts by weight proportion of micron chitosan sol and Nano chitosan colloidal sol is 6: 4.
As the preferred solution of the invention, (micron chitosan sol and Nano chitosan colloidal sol) mixture butt and polycyclic oxygen
The parts by weight proportion of ethane is 6: 1.5.
As the preferred solution of the invention, (micron chitosan sol and Nano chitosan colloidal sol) mixture butt and olefines
The parts by weight proportion of copolymer emulsion butt (commercial goods) is 1: 1.
Embodiment 1
The preparation process of Nano chitosan composite lithium battery membrane are as follows:
1. 1.5 grams of polyethylene oxide resins and 100 grams of deionized waters are being dispersed by force Forced Dispersion 30 at room temperature Chi Zhonghe
Minute, polyethylene oxide aqueous solution is made and expects for A, it is spare.
2. by 120 grams using in following Chinese invention patents (patent No.: ZL 02113792.6) claim 4, second
What the B material (micron chitosan sol) of step synthesis and 80 grams of Chinese invention patents (patent No.: ZL 200410081608.8) synthesized
The mixture of end product (Nano chitosan colloidal sol) preparation, expects for B, spare.
3. the B material by 200 grams is placed in reaction kettle, at room temperature and under the conditions of 500 revs/min of Forced Dispersions, by 10 grams of A
Material is directly added in B material reaction kettle, after A material adds, is kept 20 minutes under the conditions of, is expected again for C.
4. 205 grams of C is expected at room temperature and under the conditions of 500 revs/min of Forced Dispersions, by the charging speed of 20 gram/minutes
30 grams of styrene-acrylic latex (commercial goods), is gradually added in C material kettle by degree, waits upon after styrene-acrylic latex (commercial goods) added,
It is kept again 1 hour under the conditions of, obtains Nano chitosan composite lithium battery membrane glue product.
5. Nano chitosan composite lithium battery membrane glue is salivated, it is uniformly distributed on a pet film, through drying (25~35
DEG C), Nano chitosan composite lithium battery membrane is formed, which is 5~60 μm.
Embodiment 2
The preparation process of Nano chitosan composite lithium battery membrane are as follows:
1. 2.5 grams of polyethylene oxide resins and 100 grams of deionized waters are being dispersed by force Forced Dispersion 30 at room temperature Chi Zhonghe
Minute, polyethylene oxide aqueous solution is made and expects for A, it is spare.
2. by 100 grams using in following Chinese invention patents (patent No.: ZL02113792.6) claim 4, second
What the B material (micron chitosan sol) of step synthesis and 100 grams of Chinese invention patents (patent No.: ZL200410081608.8) synthesized
The mixture of end product (Nano chitosan colloidal sol) preparation, expects for B, spare.
3. the B material by 215 grams is placed in reaction kettle, at room temperature and under the conditions of 500 revs/min of Forced Dispersions, by 30 grams of A
Material is directly added in B material reaction kettle, after A material adds, is kept 20 minutes under the conditions of, is expected again for C.
4. 245 grams of C is expected at room temperature and under the conditions of 500 revs/min of Forced Dispersions, by the charging speed of 20 gram/minutes
15 grams of styrene-butadiene latex (commercial goods), is gradually added in C material kettle by degree, waits upon after styrene-butadiene latex add, together under the conditions of again
It is kept for 1 hour, obtains Nano chitosan composite lithium battery membrane glue product.
5. Nano chitosan composite lithium battery membrane glue is salivated, it is uniformly distributed on a pet film, through drying (25~35
DEG C), Nano chitosan composite lithium battery membrane is formed, which is 5~60 μm.
Embodiment 3
The preparation process of Nano chitosan composite lithium battery membrane are as follows:
1. 1.0 grams of polyethylene oxide resins and 100 grams of deionized waters are being dispersed by force Forced Dispersion 30 at room temperature Chi Zhonghe
Minute, polyethylene oxide aqueous solution is made and expects for A, it is spare.
2. by 40 grams using in following Chinese invention patents (patent No.: ZL02113792.6) claim 4, second step
The end of the B material (micron chitosan sol) of synthesis and the synthesis of 160 grams of Chinese invention patents (patent No.: ZL200410081608.8)
The mixture of product (Nano chitosan colloidal sol) preparation is held, is expected for B, it is spare.
3. the B material by 200 grams is placed in reaction kettle, at room temperature and under the conditions of 500 revs/min of Forced Dispersions, by 30 grams of A
Material is directly added in B material reaction kettle, after A material adds, is kept 20 minutes under the conditions of, is expected again for C.
4. 230 grams of C is expected at room temperature and under the conditions of 500 revs/min of Forced Dispersions, by the charging speed of 20 gram/minutes
10 grams of NBR latex (40% solid content commercial goods), is gradually added in C material kettle by degree, waits upon after NBR latex added,
It is kept again 1 hour under the conditions of, obtains Nano chitosan composite lithium battery membrane glue product.
5. Nano chitosan composite lithium battery membrane glue is salivated, it is uniformly distributed on a pet film, through drying (25~35
DEG C), Nano chitosan composite lithium battery membrane is formed, which is 5~60 μm.
The application has done previous experiments to Nano chitosan composite lithium battery membrane, the results showed that
(1) in power lithium battery diaphragm industrial technology field, the preparation of Nano chitosan composite lithium battery membrane and in lithium
Application in battery is feasible；
(2) (micropore conformation diaphragm material can be effective for nanometer three-dimensional network conformation of the nano-bioactive film with ecosystem
Improve ionic conductance), internal stress free, without formative memory；
(3) such nano-sized membrane have excellent mechanical strength (circumnutating, anti-tensile, impact, flexibility) and thermal stability,
Chemical stability, electrochemical stability；
(4) such nano-sized membrane has excellent close electrolyte characteristics, hydrophily, and excellent imbibition/guarantor's liquid function can
It is in repulsion state with positive electricity lithium ion using the positive electricity characteristic of Nano chitosan film during lithium battery charge/discharge,
Under the conditions of external electric field, it is more advantageous to positive electricity lithium ion and is passed through from Nano chitosan film three-dimensional mesh, can be mentioned for lithium ion
For clear passage, and effectively electronics can be prevented to flow；
(5) due to the bleeding edge and high efficiency of nanometer diaphragm material, preparation process is easy, cost is lower (existing
This cost of production of row PP/PE class diaphragm material is 4 yuan/m2Left and right).
Specifically, to application above-described embodiment 1 prepare Nano chitosan composite lithium battery membrane lithium ion battery into
Row puncture test, specific experiment result are as shown in table 1 below.
Table 1
By above-mentioned test it is found that the application utilizes Nano chitosan composite lithium battery membrane prepared in the above embodiments,
Three-dimensional network conformation, huge specific surface area, high heat-resisting, the insulating properties of the excellent film forming, nano-scale that have (are lost
Degree of reviewing >=+300 DEG C/conventional separator≤+ 100 DEG C), high puncture stability is (under starting voltage 3904mv state and battery
After puncturing 255 seconds: voltage decline 24 DEG C of 1.74mv/ cell body real storage temperature it is invariable/battery temperature rise is " zero "), performance is high
Spend the great innovation achievements of safety.
In addition, the dimension network conformation of the nanometer cun of Nano chitosan film, porosity are up to 95% or more (conventional separator 40-
50%) suction/guarantor's electrolyte function is had more, the sheet resistance of the diaphragm is smaller and conductivity is higher.
The discharging efficiency of Nano chitosan compound film battery, up to 99.5% (conventional electricity under the conditions of year-on-year circulation 600 times
95.3%) pond is only.
Under the conditions of year-on-year circulation 600 times, the circulation internal resistance climbing of Nano chitosan compound film battery is only+3.84%
(year-on-year conventional separator battery: circulation internal resistance climbing is up to+20%-+30%), shows excellent cycle characteristics.
The application is with excellent physical, chemical property, nanometer size effect, three wiener wooden rules cun network conformational characteristics
Based on Nano chitosan material, a large amount of creative experimental study is carried out to its electrochemical properties and obtains extensive achievement, is opened up
Property Nano chitosan material is (high-temperature resistant insulating properties, high puncture test stability, extremely low to create excellent electrochemical advantage
Circulation internal resistance climbing and year-on-year 99.5% excellent discharging efficiency etc.) novel battery diaphragm material and obtain breakthrough achievement.
To sum up, from molecules level, the application creatively utilizes nanoshell sugar sub-structural features and nano-scale to imitate
It answers, based on the Nano chitosan material with excellent physical, chemical property feature, big quantity is carried out to its electrochemical characteristic
Creative experiments research, and extensive achievement is obtained, pioneeringly by Nano chitosan material to create excellent electrochemical advantage；
Since Nano chitosan and its derivative have excellent film forming, high heat resistance (weightless temperature >=300 DEG C), excellent
Physical mechanical property (tensile strength is up to 41MPa, 10.7% Young's modulus 1031MPa of elongation), the height of film forming are acidproof, resistance to
Alkali, high-insulativity, the positive electricity characteristic of the three-dimensional network form of nano-scale and the repulsion state to positive electricity lithium ion, in dispatch from foreign news agency
Under field condition, it is more advantageous to net of the carbonium from the Nano chitosan nano-scale three-dimensional network conformation with positive electricity feature
It is passed through in hole, more preferably clear passage can be provided for lithium ion mobility, provided more during lithium ion charge/discharge cycle
High conductivity.
Finally, it should be noted that the foregoing is only a preferred embodiment of the present invention, it is not intended to restrict the invention,
Although the present invention is described in detail referring to the foregoing embodiments, for those skilled in the art, still may be used
To modify the technical solutions described in the foregoing embodiments or equivalent replacement of some of the technical features.
All within the spirits and principles of the present invention, any modification, equivalent replacement, improvement and so on should be included in of the invention
Within protection scope.
Claims (7)
1. a kind of Nano chitosan composite lithium battery membrane, which is characterized in that it is molten with the Nano chitosan with three-dimensional conformation
Olefinic copolymer latex/polyethylene oxide, structure are loaded with/combined to glue/micron chitosan sol particle network as timbering material
At ionomer membrane material.
2. Nano chitosan composite lithium battery membrane according to claim 1, which is characterized in that its film thickness is 5~60 μm,
Porosity is greater than 80%.
3. Nano chitosan composite lithium battery membrane of any of claims 1 or 2, which is characterized in that preparation method include with
Lower step:
By calculation amount polyethylene oxide and calculation amount deionized water, dispersing Forced Dispersion 30 minutes at room temperature Chi Zhonghe, system by force
It is A material at polyethylene oxide aqueous solution, it is spare；
The micron chitosan sol of calculation amount and Nano chitosan colloidal sol are mixed and expected as B, it is spare；
The B material of calculation amount is placed in reaction kettle, at room temperature and under the conditions of 500 revs/min of Forced Dispersions, A material is directly added
In B material reaction kettle, after A material adds, keeps 20 minutes under the conditions of, expect for C again；
The C material of calculation amount is at room temperature and under the conditions of 500 revs/min of Forced Dispersions, by the charging rate of 20 gram/minutes, gradually
The olefinic copolymer latex of calculation amount is added in C material kettle, wait upon calculation amount olefinic copolymer latex added after, together
Under the conditions of keep again 1 hour, obtain Nano chitosan composite lithium battery membrane glue product；
It by Nano chitosan composite lithium battery membrane glue, is salivated, is uniformly distributed on a pet film, through drying, it is poly- to form nanoshell
Sugared composite lithium battery membrane, the film thickness are 5~60 μm.
4. the preparation method of Nano chitosan composite lithium battery membrane according to claim 3, which is characterized in that described poly-
Aqueous solution of ethylene oxide ratio is 100 parts by weight of deionized water, adds 1.0 parts by weight polyethylene oxide butt material.
5. the preparation method of Nano chitosan composite lithium battery membrane according to claim 3, which is characterized in that described micro-
Rice chitosan sol and the parts by weight of Nano chitosan colloidal sol proportion are 6: 4.
6. the preparation method of Nano chitosan composite lithium battery membrane according to claim 3, which is characterized in that described micro-
The parts by weight of rice chitosan sol and the Nano chitosan colloidal sol mixture butt and polyethylene oxide proportion is 6:
1.5。
7. the preparation method of Nano chitosan composite lithium battery membrane according to claim 3, which is characterized in that described micro-
The parts by weight of rice chitosan sol and the Nano chitosan colloidal sol mixture butt and the olefinic copolymer latex butt
Number proportion is 1: 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910194235.1A CN109920954A (en) | 2019-03-14 | 2019-03-14 | A kind of Nano chitosan composite lithium battery membrane and its manufacturing method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910194235.1A CN109920954A (en) | 2019-03-14 | 2019-03-14 | A kind of Nano chitosan composite lithium battery membrane and its manufacturing method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109920954A true CN109920954A (en) | 2019-06-21 |
Family
ID=66964843
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910194235.1A Pending CN109920954A (en) | 2019-03-14 | 2019-03-14 | A kind of Nano chitosan composite lithium battery membrane and its manufacturing method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109920954A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115441124A (en) * | 2021-06-04 | 2022-12-06 | 丰田自动车株式会社 | Zinc secondary battery |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013181967A1 (en) * | 2012-06-04 | 2013-12-12 | 成都中科来方能源科技有限公司 | Ion polymer membrane material, preparation process therefor and lithium secondary battery |
| CN104953069A (en) * | 2014-03-25 | 2015-09-30 | 四川禧丹佛锂电有限公司 | Nanometer chitosan compound/fiber composite diaphragm for lithium battery and preparation method of diaphragm |
| CN104953068A (en) * | 2014-03-25 | 2015-09-30 | 四川禧丹佛锂电有限公司 | Nanometer chitosan composite diaphragm of lithium battery and manufacturing method of nanometer chitosan composite diaphragm |
-
2019
- 2019-03-14 CN CN201910194235.1A patent/CN109920954A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013181967A1 (en) * | 2012-06-04 | 2013-12-12 | 成都中科来方能源科技有限公司 | Ion polymer membrane material, preparation process therefor and lithium secondary battery |
| CN104953069A (en) * | 2014-03-25 | 2015-09-30 | 四川禧丹佛锂电有限公司 | Nanometer chitosan compound/fiber composite diaphragm for lithium battery and preparation method of diaphragm |
| CN104953068A (en) * | 2014-03-25 | 2015-09-30 | 四川禧丹佛锂电有限公司 | Nanometer chitosan composite diaphragm of lithium battery and manufacturing method of nanometer chitosan composite diaphragm |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115441124A (en) * | 2021-06-04 | 2022-12-06 | 丰田自动车株式会社 | Zinc secondary battery |
| CN115441124B (en) * | 2021-06-04 | 2024-03-26 | 丰田自动车株式会社 | Zinc secondary battery |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105470515B (en) | A kind of safe lithium ion power battery anode and the lithium ion battery containing the positive pole | |
| CN103682476B (en) | Battery | |
| WO2016107239A1 (en) | Hybrid supercapacitor | |
| CN103337649B (en) | A kind of modified graphene/sulfonated poly (phenylene oxide) PEM and preparation method thereof | |
| CN104934610B (en) | A kind of lithium ion battery self-supporting flexible composite electrode material preparation method | |
| CN103603178B (en) | Coating for flexible lithium-ion battery membrane, membrane containing same and preparation method thereof | |
| EP3496184B1 (en) | Multi-core/single-shell structure gel polymer-coated diaphragm, and manufacturing method and use thereof | |
| CN112521616B (en) | Grafted ceramic powder and preparation method thereof, ceramic diaphragm and preparation method thereof, lithium ion battery, battery module and battery pack | |
| CN107873104A (en) | With tridimensional network form for the electrode of electrochemical appliance, its manufacture method and include its electrochemical appliance | |
| CN106876673B (en) | The method that one-step method prepares the core-shell structure lithium sulfur battery anode material that titanium dioxide and graphene bilayer coat altogether | |
| CN112201905A (en) | Cellulose-based lithium battery flame-retardant diaphragm and preparation method thereof | |
| CN109585759A (en) | A kind of gel-like structure lithium electric separator, preparation method and solid lithium battery | |
| CN107768729A (en) | A kind of implantation polymer particles solid electrolyte in situ and preparation method thereof | |
| CN105406072A (en) | Battery with membrane-coated electrodes | |
| CN104409770B (en) | Preparation method of polymer electrolyte containing allyl functionalized ionic liquid | |
| CN104993110A (en) | Preparation method of composite negative electrode material for lithium ion battery | |
| CN103137932A (en) | Microporous polymer isolating film having good wettability on electrolyte and preparation method | |
| CN103579627A (en) | Graphene-tin composite material, preparation method of graphene-tin composite material, lithium ion battery and preparation method of lithium ion battery | |
| CN109920954A (en) | A kind of Nano chitosan composite lithium battery membrane and its manufacturing method | |
| CN205846133U (en) | A kind of aseptate lithium ion battery | |
| JP4543442B2 (en) | Polymer particles, polymer dispersion composition, slurry for battery electrode, electrode and battery | |
| CN109494345A (en) | A kind of battery preparation method and battery promoting lithium ion battery safety performance | |
| CN105514327A (en) | Lithium polymer battery | |
| CN106252587A (en) | A kind of high safety, high performance lithium ion battery negative and battery thereof | |
| CN106099172B (en) | A kind of aseptate lithium ion battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20190621 |
|
| WD01 | Invention patent application deemed withdrawn after publication |