CN103346281B - A kind of sodium alginate base lithium battery diaphragm and preparation method thereof - Google Patents
A kind of sodium alginate base lithium battery diaphragm and preparation method thereof Download PDFInfo
- Publication number
- CN103346281B CN103346281B CN201310299965.0A CN201310299965A CN103346281B CN 103346281 B CN103346281 B CN 103346281B CN 201310299965 A CN201310299965 A CN 201310299965A CN 103346281 B CN103346281 B CN 103346281B
- Authority
- CN
- China
- Prior art keywords
- lithium battery
- sodium alginate
- battery diaphragm
- nano
- spinning
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 239000000661 sodium alginate Substances 0.000 title claims abstract description 49
- 235000010413 sodium alginate Nutrition 0.000 title claims abstract description 49
- 229940005550 sodium alginate Drugs 0.000 title claims abstract description 49
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 43
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000002131 composite material Substances 0.000 claims abstract description 19
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 13
- 239000000463 material Substances 0.000 claims abstract description 12
- 239000003792 electrolyte Substances 0.000 claims abstract description 11
- 230000008602 contraction Effects 0.000 claims abstract description 4
- 230000035699 permeability Effects 0.000 claims abstract description 4
- 239000000835 fiber Substances 0.000 claims abstract description 3
- 239000011148 porous material Substances 0.000 claims abstract description 3
- 238000009987 spinning Methods 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 11
- 229920000642 polymer Polymers 0.000 claims description 9
- 239000002202 Polyethylene glycol Substances 0.000 claims description 8
- 229920001223 polyethylene glycol Polymers 0.000 claims description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 239000000654 additive Substances 0.000 claims description 6
- 230000000996 additive effect Effects 0.000 claims description 6
- 241000206575 Chondrus crispus Species 0.000 claims description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 5
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 5
- 229910001416 lithium ion Inorganic materials 0.000 claims description 5
- 239000005543 nano-size silicon particle Substances 0.000 claims description 5
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 5
- 229920002472 Starch Polymers 0.000 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- 239000012046 mixed solvent Substances 0.000 claims description 4
- 239000002086 nanomaterial Substances 0.000 claims description 4
- 239000008107 starch Substances 0.000 claims description 4
- 235000019698 starch Nutrition 0.000 claims description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 2
- 229920002101 Chitin Polymers 0.000 claims description 2
- 108010010803 Gelatin Proteins 0.000 claims description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 2
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 2
- 239000004411 aluminium Substances 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 229910000278 bentonite Inorganic materials 0.000 claims description 2
- 239000000440 bentonite Substances 0.000 claims description 2
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Substances [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 2
- 229920006184 cellulose methylcellulose Polymers 0.000 claims description 2
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- 229920000159 gelatin Polymers 0.000 claims description 2
- 239000008273 gelatin Substances 0.000 claims description 2
- 235000019322 gelatine Nutrition 0.000 claims description 2
- 235000011852 gelatine desserts Nutrition 0.000 claims description 2
- 229910001701 hydrotalcite Inorganic materials 0.000 claims description 2
- 229960001545 hydrotalcite Drugs 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 2
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 claims description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 2
- 239000000347 magnesium hydroxide Substances 0.000 claims description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 2
- 239000010445 mica Substances 0.000 claims description 2
- 229910052618 mica group Inorganic materials 0.000 claims description 2
- 239000002121 nanofiber Substances 0.000 claims description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 2
- 229910052615 phyllosilicate Inorganic materials 0.000 claims description 2
- 229920002401 polyacrylamide Polymers 0.000 claims description 2
- 229920002635 polyurethane Polymers 0.000 claims description 2
- 239000004814 polyurethane Substances 0.000 claims description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 2
- 238000012958 reprocessing Methods 0.000 claims description 2
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 2
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 2
- 239000004575 stone Substances 0.000 claims description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 3
- 238000011031 large-scale manufacturing process Methods 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 8
- 230000004888 barrier function Effects 0.000 description 7
- 239000011259 mixed solution Substances 0.000 description 6
- -1 polyethylene Polymers 0.000 description 5
- 239000004743 Polypropylene Substances 0.000 description 4
- 229920001155 polypropylene Polymers 0.000 description 4
- 238000013019 agitation Methods 0.000 description 3
- 239000005030 aluminium foil Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000005056 compaction Methods 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 229920000098 polyolefin Polymers 0.000 description 3
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- FHVDTGUDJYJELY-UHFFFAOYSA-N 6-{[2-carboxy-4,5-dihydroxy-6-(phosphanyloxy)oxan-3-yl]oxy}-4,5-dihydroxy-3-phosphanyloxane-2-carboxylic acid Chemical compound O1C(C(O)=O)C(P)C(O)C(O)C1OC1C(C(O)=O)OC(OP)C(O)C1O FHVDTGUDJYJELY-UHFFFAOYSA-N 0.000 description 1
- 241000195493 Cryptophyta Species 0.000 description 1
- AEMOLEFTQBMNLQ-VANFPWTGSA-N D-mannopyranuronic acid Chemical compound OC1O[C@H](C(O)=O)[C@@H](O)[C@H](O)[C@@H]1O AEMOLEFTQBMNLQ-VANFPWTGSA-N 0.000 description 1
- IAJILQKETJEXLJ-UHFFFAOYSA-N Galacturonsaeure Natural products O=CC(O)C(O)C(O)C(O)C(O)=O IAJILQKETJEXLJ-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 241000199919 Phaeophyceae Species 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229940072056 alginate Drugs 0.000 description 1
- 235000010443 alginic acid Nutrition 0.000 description 1
- 229920000615 alginic acid Polymers 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 235000014633 carbohydrates Nutrition 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 235000013373 food additive Nutrition 0.000 description 1
- 239000002778 food additive Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 231100000957 no side effect Toxicity 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
- 238000009736 wetting 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
Landscapes
- Cell Separators (AREA)
- Secondary Cells (AREA)
Abstract
The invention belongs to lithium battery diaphragm technical field, particularly relate to a kind of sodium alginate base lithium battery diaphragm and preparation method thereof.Lithium battery diaphragm of the present invention is with sodium alginate base composite non woven film for base material, adopts electrostatic spinning process to prepare.Sodium alginate base lithium battery diaphragm thickness prepared by the present invention is 10 μm-300 μm, fibre diameter is 20nm-2000nm, air permeability is 1s-600s/100cc, porosity is 40%-90%, pore diameter range is 0.02 μm-4 μm, electrolyte absorptivity is 150%-900%, and thermal stability is excellent, 150
o?at C temperature, dimensional contraction rate is less than 0.5%.Sodium alginate base lithium battery diaphragm function admirable provided by the present invention, there is the electrochemical stability performance of higher ionic conductivity, suitable mechanical strength and excellence, and the interface stability performance improved between itself and positive and negative pole material, drastically increases the high rate performance of lithium battery, long circulation life and security performance.Meanwhile, provided by the present invention preparation is simple, and low production cost is easy to large-scale production.
Description
Technical field
The present invention relates to a kind of sodium alginate base lithium battery diaphragm; The invention still further relates to the preparation method of above-mentioned sodium alginate base lithium battery diaphragm.
Background technology
Lithium battery forms primarily of positive and negative pole material, electrolyte and barrier film.Barrier film, between lithium ion battery plus-negative plate material, is one of important composition parts of lithium ion battery.The effect of barrier film is extremely important, plays isolated both positive and negative polarity, prevents internal short-circuit of battery, simultaneously stability electrolyte, completes lithium ion important function such as fast transport between both positive and negative polarity in charge discharge process.Along with the development of lithium battery, more and more higher to the requirement of membrane properties, the quality of its performance directly has influence on the charge-discharge performance of lithium battery, service life cycle, high temperature performance and security performance etc.The proportion that barrier film cost accounts for battery total cost is 20%-30%, and in dynamic lithium battery, proportion is higher.Therefore barrier film cost is reduced significant to reduction battery total cost.At present, commercial lithium battery diaphragm material mainly polyolefin micropore polymer film, comprises polyethylene film, polypropylene screen and polyethylene-polypropylene biaxial stretching film.Polyolefin micropore barrier diaphragm no doubt has oneself advantage: such as have good electrochemical stability performance and suitable mechanical strength.Certainly also there is shortcomings: (1) electrolyte wetting property bad electrolyte absorptivity is low, limits the raising of ionic conductivity, is unfavorable for the fast charging and discharging of lithium battery; (2) thermal dimensional stability can be poor, in temperature higher than 120
othere will be significant dimensional contraction during C, inside battery is short-circuited.These limit the further application of polyolefin micropore barrier diaphragm to a certain extent.In addition, polyolefinic raw material sources, in petroleum resources, belong to non-renewable resources, and cost compare is high, and nearest lithium electricity security incident intense stimulus high-temperature-resistant membrane market, therefore developing low-cost, lithium battery diaphragm that is renewable and high safety performance just seem and are even more important.
1881, first Englishize scholar carried out scientific research to the alginate extract in brown seaweed.Sodium alginate derives from the algae such as the brown alga in ocean, is a kind of reproducible resource.Sodium alginate is soluble in water, forms viscous liquid.Sodium alginate is a kind of natural polysaccharide carbohydrate, there is carboxyl, it is the high polyuronide that the aldehyde radical of mannuronic acid is formed with glycosidic bond, there is excellent biocompatibility, have no side effect, the feature such as controlled biological degradability, nonreactive substance, just because of the performance of these excellences, make sodium alginate can be used as food additives, thickener, stabilizer, weaving dyeing auxiliaries, styptic, also can be used as the fields such as Medical rack material.At present, sodium alginate have also been obtained in electrochemical field and applies widely, as the binding agent of electrode material of lithium battery, greatly can promote the stability of circulating battery, also can be used for the fields such as ultracapacitor.But as far as we know, so far not about the report of sodium alginate base lithium battery diaphragm.Given this, the present invention utilizes electrostatic spinning process successfully to prepare sodium alginate base composite non woven film, and is applied to the fields such as lithium battery diaphragm.
Summary of the invention
The object of the present invention is to provide a kind of sodium alginate base lithium battery diaphragm, improve the properties of existing battery diaphragm.
Another object of the present invention is to provide the method preparing sodium alginate base lithium battery diaphragm.
For achieving the above object, sodium alginate base lithium battery diaphragm provided by the invention is sodium alginate base composite non woven film, film thickness is 10 μm-300 μm, fibre diameter is 20nm-2000nm, and air permeability is 1s-600s/100cc, and porosity is 40%-90%, pore diameter range is 0.02 μm-4 μm, electrolyte absorptivity is 150%-900%, and thermal stability is excellent, 150
oat C temperature, dimensional contraction rate is less than 0.5%.
For achieving the above object, the preparation method that the present invention takes carries out electrostatic spinning to mixed solution of sodium alginate, and experimental procedure is as follows:
A. prepare polymer solution: sodium alginate, additive and solvent are mixed with certain density polymer solution, eliminate bubble, stand for standby use;
B. electrostatic spinning is carried out to polymer solution: the polymer solution prepared by step a injects electrostatic spinning machine, regulate the distance between spinning syringe needle and dash receiver, start electrostatic spinning;
C. reprocessing: by the sodium alginate based nano-fiber film roll-in of arriving of electrostatic spinning, drying, obtain sodium alginate base composite non woven film.
In wherein said preparation method, sodium alginate mass percent is 0.1%-50%, and additive mass percent is 0.1%-50%, and solvent for use is the mixed solvent of water or water.Other solvents in mixed solvent are the solvent dissolved each other with water, and as one or more in methyl alcohol, ethanol, glycerol, acetone, formic acid, acetic acid, oxolane, the ratio of solvent and water is for being 0.1%-99%.Described additive is macromolecular material or inorganic nano material.Macromolecular material comprises but is not only confined to acetic starch, hydroxymethyl starch, sodium carboxymethylcellulose, one or more in CMC, gelatin, carragheen, shitosan, chitin, polyvinyl alcohol, polyethylene glycol oxide, soluble polyurethane, polyacrylamide or polyvinylpyrrolidone; Inorganic nano material comprise but be not only confined in nano-calcium carbonate, nano barium sulfate, nano imvite, nano silicon, nano titanium oxide, nano-aluminium oxide, nano zirconium dioxide, mica sheet, imvite, bentonite, phyllosilicate, layered double hydroxide, hydrotalcite, the thin aluminium stone of plan, stratiform disulphide, magnesium hydroxide one or more.
In wherein said preparation method, the spinning syringe needle internal diameter of electrostatic spinning is 0.2mm-4.0mm, and voltage is 1kV-40kV; The distance of syringe needle and receiving system is 2cm-40cm, and spinning temperature is 20
oc-90
oc, spinning flow is 0.05mL/h-10mL/h, and the intensity of mechanical roll-in is 0.5MPa-30MPa, time of staying 1min-20min, and roll temperature is 20
oc-100
oc.
The purposes of sodium alginate base lithium battery diaphragm is: the sodium alginate base composite non woven film adopting close electrolyte is base material, improve the electrolyte uptake of lithium battery diaphragm, this composite non woven film has higher ionic conductivity and suitable mechanical strength simultaneously, drastically increases the high rate performance of lithium battery, long circulation life and security performance.Therefore this composite non woven film can be applicable to the fields such as lithium metal battery (comprising lithium-sulfur cell), lithium ion power and energy-storage battery.
Accompanying drawing explanation
Fig. 1 is the chemical constitution schematic diagram of sodium alginate.
Fig. 2 is the stereoscan photograph on sodium alginate/polyethylene glycol oxide composite non woven film surface prepared by the embodiment of the present invention 1.
Fig. 3 is the charging and discharging curve figure after the sodium alginate/polyethylene glycol oxide composite non woven film assembling lithium metal battery of preparation in embodiment 1.
Fig. 4 is the long circulating curve chart after the sodium alginate/polyethylene glycol oxide composite non woven film assembling lithium-sulfur cell of preparation in embodiment 1.
Embodiment
Be more than to of the present invention generality describe, below we will be further explained claim of the present invention by specific embodiment.
Embodiment 1
Take 1.5g sodium alginate respectively, 1.5g polyethylene glycol oxide is dissolved in 97g deionized water, after magnetic agitation 2h, obtain homogeneous sodium alginate/polyethylene glycol oxide mixed solution.Take out 2mL mixed solution and be placed in syringe, syringe needle internal diameter is 1.2mm.Aluminium-foil paper is as receiving system, and presetting spinning condition is: fixed voltage 15kV, constant spacing 10cm, fixed solution flow 0.5mL/h.By the pressure compaction tunica fibrosa of tunica fibrosa 8MPa after spinning terminates, obtain sodium alginate/polyethylene glycol oxide composite non woven film that thickness is 30 μm.
Embodiment 2
Take 2g sodium alginate, 1g polyvinyl alcohol dissolution respectively in 80g deionized water, magnetic agitation obtains homogeneous sodium alginate/polyvinyl alcohol mixing solution after stirring 3h.Take out 2.5mL gained mixed solution in syringe, syringe needle internal diameter is 0.8mm.Aluminium-foil paper is as receiving system, and presetting spinning condition is: fixed voltage 30kV, constant spacing 15cm, fixed solution flow 1mL/h.By the pressure compaction tunica fibrosa of tunica fibrosa 10MPa after spinning terminates, obtain the ALG sodium/polyvinyl alcohol composite non woven film of thickness 50 μm.
Embodiment 3
Taking 3g sodium alginate, 2g carragheen and 2g nano silicon is respectively dissolved in 150g deionized water, and magnetic agitation obtains homogeneous sodium alginate/carragheen/nano silicon mixed solution after stirring 4h.Take out 4mL gained mixed solution in syringe, syringe needle internal diameter is 1.6mm.Aluminium-foil paper is as receiving system, and presetting spinning condition is: fixed voltage 25kV, constant spacing 20cm, fixed solution flow 2mL/h.By the pressure compaction tunica fibrosa of tunica fibrosa 5MPa after spinning terminates, obtain sodium alginate/carragheen/nano silicon composite non woven film that thickness is 70 μm.
The present invention is not only confined to above execution mode, can prepare meet product type required for lithium battery diaphragm and specification according to material proportion, spinning voltage, spinning temperature, receiving range, rolling pressure, roll-in time and roll temperature etc.The scientific research personnel of this area can also make various change and distortion, under the prerequisite of this patent purport, all in the scope of this patent.
Comparative example: adopt business-like polypropylene diaphragm as a comparison, to illustrate the advantage of the sodium alginate base lithium battery diaphragm described in this patent further.
Sodium alginate base composite non woven film obtained by embodiment 1-3 and the polypropylene diaphragm in comparative example are carried out to the sign of thickness, porosity, gas permeability, electrolyte absorptivity, hot strength, thermal stability, surface topography and battery performance, result is as shown in table 1, Fig. 2 and Fig. 3.Be not difficult to draw: the sodium alginate base lithium battery diaphragm that this patent provides has that porosity is high, electrolyte absorb many, thermal stability good, mechanical strength is suitable, charging and discharging curve is stable and the advantage such as good cycling stability, meets the requirement of high-performance lithium battery diaphragm.
Table 1
Claims (9)
1. a lithium battery diaphragm, it is characterized in that: described battery diaphragm is sodium alginate base composite non woven film, the preparation process of sodium alginate base composite non woven film is as follows: a. prepares polymer solution: sodium alginate, additive and solvent are mixed with certain density polymer solution, eliminate bubble, stand for standby use; B. electrostatic spinning is carried out to polymer solution: the polymer solution prepared by step a injects electrostatic spinning machine, regulate the distance between spinning syringe needle and dash receiver, start electrostatic spinning; C. reprocessing: the sodium alginate based nano-fiber film roll-in obtained by electrostatic spinning, drying, obtain sodium alginate base composite non woven film.
2. lithium battery diaphragm according to claim 1, it is characterized in that: described sodium alginate base composite non woven film thickness is 10 μm-300 μm, fibre diameter is 20nm-2000nm, air permeability is 1s-600s/100cc, porosity is 40%-90%, pore diameter range is 0.02 μm-4 μm, and electrolyte absorptivity is 150%-900%.
3. lithium battery diaphragm according to claim 1, is characterized in that: described sodium alginate base composite non woven film is 150
oat C temperature, dimensional contraction rate is less than 0.5%.
4. lithium battery diaphragm according to claim 1, is characterized in that: in a polymer solution, and the mass percent of sodium alginate is 0.1%-50%, and the mass percent of additive is 0.1%-50%.
5. lithium battery diaphragm according to claim 1, it is characterized in that: solvent for use is the mixed solvent of water or water, other solvents in mixed solvent are the solvent dissolved each other with water, other solvents are one or more in methyl alcohol, ethanol, glycerol, acetone, formic acid, acetic acid, oxolane, and the ratio of solvent and water is 0.1%-99%.
6. lithium battery diaphragm according to claim 1, it is characterized in that: described additive is macromolecular material or inorganic nano material, macromolecular material comprises acetic starch, hydroxymethyl starch, sodium carboxymethylcellulose, CMC, gelatin, carragheen, shitosan, chitin, polyvinyl alcohol, polyethylene glycol oxide, one or more in soluble polyurethane, polyacrylamide or polyvinylpyrrolidone; Inorganic nano material comprise in nano-calcium carbonate, nano barium sulfate, nano silicon, nano titanium oxide, nano-aluminium oxide, nano zirconium dioxide, mica sheet, imvite, bentonite, phyllosilicate, layered double hydroxide, hydrotalcite, the thin aluminium stone of plan, stratiform disulphide, magnesium hydroxide one or more.
7. lithium battery diaphragm according to claim 1, is characterized in that: the spinning syringe needle internal diameter of electrostatic spinning is 0.2mm-4.0mm, and voltage is 1kV-40kV, and the distance of syringe needle and receiving system is 2cm-40cm, and spinning temperature is 20
oc-90
oc, spinning flow is 0.05mL/h-10mL/h.
8. lithium battery diaphragm according to claim 1, is characterized in that: the intensity of mechanical roll-in is 0.5MPa-30MPa, time of staying 1min-20min, and roll temperature is 20
oc-100
oc.
9. the application of lithium battery diaphragm according to claim 1 in lithium metal battery, lithium ion battery.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310299965.0A CN103346281B (en) | 2013-07-17 | 2013-07-17 | A kind of sodium alginate base lithium battery diaphragm and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310299965.0A CN103346281B (en) | 2013-07-17 | 2013-07-17 | A kind of sodium alginate base lithium battery diaphragm and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103346281A CN103346281A (en) | 2013-10-09 |
| CN103346281B true CN103346281B (en) | 2016-04-13 |
Family
ID=49281064
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310299965.0A Active CN103346281B (en) | 2013-07-17 | 2013-07-17 | A kind of sodium alginate base lithium battery diaphragm and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103346281B (en) |
Families Citing this family (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104716301A (en) * | 2013-12-11 | 2015-06-17 | 上海空间电源研究所 | Positive electrode of lithium-sulfur battery and manufacturing method of positive electrode |
| CN104241572B (en) * | 2014-09-19 | 2017-10-10 | 安科智慧城市技术（中国）有限公司 | A kind of preparation method, film and the battery of alkaline solid polymer electrolyte tunica fibrosa |
| WO2017113275A1 (en) * | 2015-12-31 | 2017-07-06 | 宁波艾特米克锂电科技有限公司 | Composite nanofiber membrane for electrochemical element, preparation method and energy storage device |
| CN106128794A (en) * | 2016-06-24 | 2016-11-16 | 安徽江威精密制造有限公司 | The aging resistance ultracapacitor composite diaphragm material that a kind of weatherability is good |
| CN107516722A (en) * | 2017-07-20 | 2017-12-26 | 河南师范大学 | Alginate dressing is used as the method for modifying of lithium battery diaphragm |
| CN108060469B (en) * | 2017-12-30 | 2021-04-16 | 安徽宏祥丝绸织造有限公司 | Preparation method of stretch-proof spandex fiber for heavy crepe |
| CN108767174A (en) * | 2018-06-11 | 2018-11-06 | 佛山腾鲤新能源科技有限公司 | A kind of preparation method of Organic-inorganic composite lithium battery diaphragm |
| CN109088032A (en) * | 2018-06-28 | 2018-12-25 | 中国地质大学（武汉） | A kind of polyvinyl alcohol lithium battery diaphragm and preparation method thereof based on chitosan |
| CN110735232B (en) * | 2018-07-18 | 2021-12-24 | 中国科学院宁波材料技术与工程研究所 | Fiber material and preparation method and application thereof |
| CN109192906B (en) * | 2018-09-19 | 2020-12-15 | 中国科学技术大学 | Preparation method of organic-inorganic nano composite battery diaphragm |
| CN109273643A (en) * | 2018-09-25 | 2019-01-25 | 合肥先杰新能源科技有限公司 | The preparation method of lithium battery fire-retardant cellulose diaphragm |
| CN109244329A (en) * | 2018-09-25 | 2019-01-18 | 合肥先杰新能源科技有限公司 | The preparation method of fiber base lithium ion battery separator |
| CN109494365A (en) * | 2018-11-09 | 2019-03-19 | 南昌大学 | A kind of preparation method of the LDH- porous charcoal sulphur composite material for lithium-sulphur cell positive electrode |
| CN109742297A (en) * | 2018-12-29 | 2019-05-10 | 江西省通瑞新能源科技发展有限公司 | A kind of method that modified alta-mud prepares lithium battery diaphragm |
| CN112259911B (en) * | 2020-09-30 | 2021-08-06 | 上海恩捷新材料科技有限公司 | Electrochemical device, non-woven fabric ceramic diaphragm and preparation method thereof |
| CN114256560A (en) * | 2021-11-24 | 2022-03-29 | 中国科学院宁波材料技术与工程研究所 | Cellulose inorganic composite membrane, high-temperature-resistant battery diaphragm, and preparation method and application thereof |
| CN114665195A (en) * | 2022-03-16 | 2022-06-24 | 苏州大学 | Flexible air battery and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102522515A (en) * | 2011-12-22 | 2012-06-27 | 中国科学院青岛生物能源与过程研究所 | Cellulose/polymer fiber composite diaphragm material for lithium secondary battery and preparation method thereof |
| CN102969471A (en) * | 2012-10-24 | 2013-03-13 | 中国科学院青岛生物能源与过程研究所 | High-temperature resistant aromatic polysulfonamide base lithium ion battery diaphragm |
-
2013
- 2013-07-17 CN CN201310299965.0A patent/CN103346281B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102522515A (en) * | 2011-12-22 | 2012-06-27 | 中国科学院青岛生物能源与过程研究所 | Cellulose/polymer fiber composite diaphragm material for lithium secondary battery and preparation method thereof |
| CN102969471A (en) * | 2012-10-24 | 2013-03-13 | 中国科学院青岛生物能源与过程研究所 | High-temperature resistant aromatic polysulfonamide base lithium ion battery diaphragm |
Non-Patent Citations (1)
| Title |
|---|
| "A Heat-Resistant Silica Nanoparticle Enhanced Polysulfonamide Nonwoven Separator for High-Performance Lithium Ion Battery";Jianjun Zhang 等;《Journal of The Electrochemical Society》;20130308;第160卷(第6期);摘要，第769页右栏第3段-第771页右栏倒数第1段和表1、图2-4以及结论 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103346281A (en) | 2013-10-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103346281B (en) | A kind of sodium alginate base lithium battery diaphragm and preparation method thereof | |
| Boriboon et al. | Cellulose ultrafine fibers embedded with titania particles as a high performance and eco-friendly separator for lithium-ion batteries | |
| CN102585280B (en) | Preparation method of carbon material modified porous polymer electrolyte membrane | |
| CN107959049B (en) | Preparation method of gel electrolyte, gel electrolyte and lithium ion battery | |
| CN104183867B (en) | A kind of single ion conductor nano-particle reinforcement lithium battery diaphragm or method for preparing polymer electrolytes and application | |
| CN104157815B (en) | A kind of Bacterial cellulose porous membrane and preparation method thereof | |
| CN102969471B (en) | A kind of high-temperature resistant aromatic polysulfonamide base lithium ion battery diaphragm | |
| CN102263290B (en) | Polymer battery and preparation method thereof | |
| CN102516585B (en) | Biomass cellulose porous composite diaphragm used for lithium ion secondary cell | |
| WO2016095771A1 (en) | Composite nanofiber separator with thermal shutdown function, preparation method therefor and energy storage components | |
| CN105218992B (en) | sulfonated graphene metal salt solid polymer electrolyte and its preparation method and application | |
| CN108063279A (en) | A kind of cellulose base gel polymer electrolyte and preparation method thereof and the lithium ion battery containing the electrolyte | |
| CN113150314B (en) | Composite gel electrolyte material with interpenetrating network porous structure, preparation and application thereof | |
| CN104752663A (en) | Preparation method of fluorine-containing polymer porous nano-micron fibre electrode diaphragm | |
| CN103618056A (en) | Preparation method of nano-fiber membrane with three-dimensional porous structure for lithium ion battery diaphragm | |
| CN103578774B (en) | A kind of preparation method of electrode of super capacitor | |
| CN103730619B (en) | A kind of preparation method of diaphragm for lithium ion battery of high strength | |
| CN104466063A (en) | Polydopamine surface modified polyether sulfone nanofiber composite diaphragm and preparation method and applications | |
| CN104681864A (en) | Gel type polymer electrolyte with high energy density and high ionic conductivity | |
| CN103872282A (en) | Polymer lithium ion battery diaphragm and preparation method thereof | |
| CN105161762A (en) | Preparation method of polymer electrolyte membrane and lithium-ion battery | |
| CN106298254A (en) | Polyaniline/porous metal film material, anode composite pole piece, preparation method and application | |
| Deng et al. | 3D-cellulose acetate-derived hierarchical network with controllable nanopores for superior Li+ transference number, mechanical strength and dendrites hindrance | |
| CN103137932A (en) | Microporous polymer isolating film having good wettability on electrolyte and preparation method | |
| CN109244329A (en) | The preparation method of fiber base lithium ion battery separator |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20231123 Address after: The first and second floors of Building 2, Qingdao Belong Science and Technology Innovation Park, No. 120 Zhuzhou Road, Laoshan District, Qingdao City, Shandong Province, 266101 Patentee after: Zhongke Shenlan Huize New Energy (Qingdao) Co.,Ltd. Address before: 266101 box 30, 189 Songling Road, Laoshan District, Qingdao City, Shandong Province Patentee before: QINGDAO INSTITUTE OF BIOENERGY AND BIOPROCESS TECHNOLOGY, CHINESE ACADEMY OF SCIENCES |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20240108 Address after: Room 701, No. 18 Xinya Road, Wujin National High tech Industrial Development Zone, Changzhou City, Jiangsu Province, 213164 Patentee after: Zhongke Shenlan Huize New Energy (Changzhou) Co.,Ltd. Address before: The first and second floors of Building 2, Qingdao Belong Science and Technology Innovation Park, No. 120 Zhuzhou Road, Laoshan District, Qingdao City, Shandong Province, 266101 Patentee before: Zhongke Shenlan Huize New Energy (Qingdao) Co.,Ltd. |
|
| TR01 | Transfer of patent right |