CN103342829B - Preparation method of lithium ion battery separator - Google Patents
Preparation method of lithium ion battery separator Download PDFInfo
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- CN103342829B CN103342829B CN201310276765.3A CN201310276765A CN103342829B CN 103342829 B CN103342829 B CN 103342829B CN 201310276765 A CN201310276765 A CN 201310276765A CN 103342829 B CN103342829 B CN 103342829B
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- 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 discloses a preparation method of a lithium ion battery separator, comprising the following steps of: (1) preparing polymer nanoparticles; (2) preparing a film casting liquid, namely evenly mixing one or a mixture of polymer polyvinylidene fluoride, cellulose, non-woven fabrics, polyvinylidene fluoride-hexafluoropropylene, polyacrylonitrile or polyving akohol and a diluent based on a mass ratio of 1: (1-15), adding polymer nanoparticles accounting for 2-50% of the weight of the polymer, stirring and heating in water bath to obtain the film casting liquid; (3) molding: performing curtain coating on the film casting liquid to obtain a rudiment mold; and (4) posttreatment: immersing the rudiment mold in water or an organic solvent normal hexane, cyclohexane, absolute ethyl alcohol, methanol, methylbenzene or xylene, removing the diluent in the separator, and vacuum drying to obtain the separator. The lithium ion battery separator prepared by the invention has good contact property with an electrolyte, excellent electrochemical stability, high ionic conductivity and small impedance.
Description
Technical field
The present invention relates to a kind of preparation method of lithium ion battery separator, especially relate to a kind of preparation method of the lithium ion battery separator containing polymer nano granules.
Background technology
Barrier film, as one of most important parts of lithium ion battery, is referred to as " the 3rd pole " of battery, and major function is isolation positive and negative electrode, prevents directly contact and is short-circuited, simultaneously for the to-and-fro movement of lithium ion provides passage.The barrier film being widely used in lithium ion battery is at present mainly polyalkene diaphragm, and its preparation technology divides dry method and wet method two kinds.The maximum defect of polyalkene diaphragm is that the contact of organic electrolyte is poor, is not easily soaked by electrolytic solution, has a strong impact on the raising of ionic conductivity.
Polymer nano material is causing increasing concern, and polymer nano granules not only possesses the property such as small-size effect, surface effects of conventional inorganic nano particle, also can show its characteristic as macromolecular compound simultaneously.At present, the preparation method of polymer nano granules mainly comprises exchange of solvent method and emulsion polymerization, for improving solid content, often needs to add a certain amount of tensio-active agent in process.
CN101824118B discloses a kind of porous polymer nanoparticles and preparation method thereof, the method adopts emulsion polymerization polymerizing styrene class monomer and divinylbenzene monomers, obtain monodisperse porous polymer nanoparticle precursor, again by the method for interior crosslinked or external crosslinking by super for monodisperse porous polymer nanoparticle precursor crosslinked, acquisition monodisperse porous polymer nano particle.Adopt this method can prepare the polymer beads of particle diameter at the size tunable of 20-200nm.
CN1276930C discloses a kind of non-emulsion process preparing the polymer nano granules of high solids content, and it improves solid content by mode that pulse is reinforced, this method can prepare solid content up to 45% polymer nano granules.
At present, the kind of lithium ion battery separator is mainly polyolefin film and polyvinylidene difluoride (PVDF) and the blend film with respective compound thereof, wherein also have and mix inorganic nanoparticles to strengthen barrier film intensity in film-casting liquid, but but report is rarely had for the application of polymer nano granules in lithium ion battery separator.
US4588633 discloses a kind of lithium ion battery separator preparation method, and the method ultrahigh molecular weight polyethylene(UHMWPE) and mineral oil is added by a certain percentage in stirrer to carry out stirring and dissolving, and wherein, mineral oil and poly ratio are 10-99:1.Above-mentioned formula can strengthen every film strength, also substantially meets the requirement of lithium ion battery to barrier film, but there is following defect: the diaphragm micro-hole aperture of formation is uneven, and then affects its performance in the battery.
CN101212036A discloses a kind of microporous polymer isolating film for Li-ion battery and preparation method thereof, this barrier film take water as reaction medium, polyvinyl alcohol, hydrophilic monomer and hydrophobic monomer by initiator in aqueous initiated polymerization obtain polymer latex precursor emulsion, adopt cast coat technique, be coated in plastics base band, stripping and get final product after dry.The micropore of gained barrier film both can't help stretching and had been caused, and also do not need solvent extraction, its pore-forming principle is microphase-separated method.The standby barrier film porosity of this legal system is high, aperture is little, effectively can prevent battery short circuit, and ionic conductivity and thermostability all can meet the use of lithium ion battery simultaneously.But be limited to used material, its barrier film decomposition voltage is on the low side, and electrochemical stability is desirable not enough.
Summary of the invention
Technical problem to be solved by this invention is, provides a kind of ionic conductivity, the preparation method of all improved lithium ion battery separator of thermostability and electrochemical stability.
The technical solution adopted for the present invention to solve the technical problems is: a kind of preparation method of lithium ion battery separator, comprises the following steps:
(1) preparation of polymer nano granules: the mixture of one or more in the polymkeric substance such as polyethylene, polystyrene, polymethyl acrylic acid acid methyl esters, polyacrylic acid, polyacrylic ester or polypropylene is made polymer nano granules by exchange of solvent method or emulsion polymerization, and the particle diameter of described polymer nano granules is the preferred 50-300nm of 10-500nm();
(2) preparation of film-casting liquid: by the mixture of one or more in polymer polyvinylidene fluoride, Mierocrystalline cellulose, non-woven fabrics, polyvinylidene difluoride (PVDF)-R 1216, polyacrylonitrile or polyvinyl alcohol etc. and the thinner preferred 1:4-9 of 1:1-15(in mass ratio) ratio mix, then add and be equivalent to the preferred 10-30% of polymer weight 2-50%() polymer nano granules, in 30-50 DEG C of stirred in water bath heating 3-6h, obtain film-casting liquid;
(3) shaping: step (2) gained film-casting liquid curtain coating is become blank film, leave standstill 1-3h;
(4) aftertreatment: be immersed in the water or immerse in the organic solvents such as normal hexane, hexanaphthene, dehydrated alcohol, methyl alcohol, toluene or dimethylbenzene (for nonaqueous diluents), removes the thinner in barrier film, vacuum-drying.
Further, in step (2), described thinner is the mixture of one or more in N-N,N-DIMETHYLACETAMIDE (DMAc), dibutyl phthalate (DBP) or N-Methyl pyrrolidone.
Further, in step (2), before mixing, be also added with the inorganic particles such as nano-silicon, nano silicon, nano aluminium oxide or nano-calcium carbonate, particle diameter is 20-200nm, and addition is the preferred 2.5-4.5% of 0.05-5.0%(of polymer weight).
Further, in step (3), the matrix of film-casting liquid curtain coating is smooth glass plate or stainless steel plate, casting temperature 40-80 DEG C; The thickness of gained blank film is 10-100 μm.
When adopting exchange of solvent legal system for polymer nano granules, principle that is nontoxic, cheap, wide material sources is followed in the right selection of strong and weak solvent, and the non-solvent of normal employing comprises alcohol, aromatic ester class or distilled water.When adopting emulsion polymerization to prepare polymer nano granules; generally choose the reaction system that reaction conditions gentleness, processing ease realization etc. are easy to large-scale production; emulsifying agent is selected from alkylsulfonate, alkyl biphenyl base ether sulfonate and conventional surfactant, and initiator is selected from persulphate.
The present invention by adding polymer nano granules to improve barrier film ionic conductivity, the performance such as thermostability and physical strength in lithium ion battery separator matrix, thus obtained modification lithium-ion battery barrier film.
Embodiment
Below in conjunction with embodiment, the invention will be further described.
Embodiment 1
The present embodiment comprises the following steps:
(1) preparation of polymer nano granules: nano-polyethylene polyethylene being made median size 100 nm by exchange of solvent method;
(2) preparation of film-casting liquid: take 2.00g polyvinylidene difluoride (PVDF) (PVDF) and 18.00g N-N,N-DIMETHYLACETAMIDE (DMAc) in 100ml Erlenmeyer flask, after stirring, add 0.2g nano-polyethylene, at 40 DEG C of stirred in water bath heating 5h, obtains film-casting liquid;
(3) shaping: step (2) gained film-casting liquid curtain coating on smooth glass plate is become blank film, casting temperature 50 DEG C, film thickness is 100 microns, leave standstill 1h;
(4) aftertreatment: be immersed in the water realization and be separated and obtain barrier film, dry 5h at then barrier film being put into vacuum drying oven 60 DEG C.
The pick up of gained barrier film reaches 200%, and specific conductivity reaches 2.5 ms/cm, septum body resistance 3 Ω, electrochemical stability window 4.7V, and barrier film intensity (transverse tensile strength 23 MPa, longitudinal tensile strength 100 MPa) meets battery assembling demand.
Embodiment 2
The present embodiment comprises the following steps:
(1) preparation of polymer nano granules: nanometer polymethylmethacrylate polyethylene being made median size 60 nm by exchange of solvent method;
(2) preparation of film-casting liquid: take 2.00g polyvinylidene difluoride (PVDF)-R 1216 (PVDF-HFP) and 8.00g dibutyl phthalate (DBP) in 100ml Erlenmeyer flask, after stirring, add 0.35g nanometer polymethylmethacrylate, at 60 DEG C of stirred in water bath heating 3h, obtain film-casting liquid;
(3) shaping: step (2) gained film-casting liquid curtain coating on smooth glass plate is become blank film, casting temperature 40 DEG C, film thickness is 100 microns, leave standstill 3h;
(4) aftertreatment: immerse in dehydrated alcohol and realize being separated obtaining barrier film, then barrier film is put into 60 DEG C of vacuum drying ovens and dry 5h.
The pick up of gained barrier film reaches 250%, and specific conductivity reaches 3.2ms/cm, septum body resistance 3.2 Ω, electrochemical stability window 4.7V, and barrier film intensity (transverse tensile strength 25MPa, longitudinal tensile strength 112MPa) meets battery assembling demand.
Embodiment 3
The present embodiment comprises the following steps:
(1) preparation of polymer nano granules: nanometer polymethylmethacrylate polyethylene being made median size 60 nm by exchange of solvent method;
(2) preparation of film-casting liquid: take 2.00g polyvinylidene difluoride (PVDF) (PVDF) and 18.00g N-N,N-DIMETHYLACETAMIDE (DMAc) in 100ml Erlenmeyer flask, after stirring, add 0.50g nanometer polymethylmethacrylate, in 40 DEG C of stirred in water bath heating 5h, obtain film-casting liquid;
(3) shaping: step (2) gained film-casting liquid curtain coating on smooth glass plate is become blank film, casting temperature 55 DEG C, film thickness is 100 microns, leave standstill 1h;
(4) aftertreatment: be immersed in the water realization and be separated and obtain barrier film, then barrier film is placed in 60 DEG C of vacuum drying ovens and dries 5h.
The pick up of gained barrier film reaches 320%, and specific conductivity reaches 3.6ms/cm, septum body resistance 2.5 Ω, electrochemical stability window 4.7V, and barrier film intensity (transverse tensile strength 28MPa, longitudinal tensile strength 107MPa) meets battery assembling demand.
Embodiment 4
The present embodiment comprises step:
(1) preparation of polymer nano granules: nanometer polymethylmethacrylate polyethylene being made median size 60 nm by exchange of solvent method;
(2) preparation of film-casting liquid: take 2.00g polyvinylidene difluoride (PVDF) (PVDF), 0.060g nanometer silicon dioxide particle (median size is 100nm), 17.7.00g N-Methyl pyrrolidone (NMP) in 100ml Erlenmeyer flask, after stirring, add 0.30g nanometer polymethylmethacrylate, in 40 DEG C of stirred in water bath heating 5h, obtain film-casting liquid;
(3) shaping: step (2) gained film-casting liquid curtain coating on smooth glass plate is become blank film, casting temperature 60 DEG C, film thickness is 100 microns, leave standstill 1h;
(4) aftertreatment: immerse in dehydrated alcohol and realize being separated obtaining barrier film, then barrier film is placed in 60 DEG C of vacuum drying ovens and dries 5h.
The pick up of gained barrier film reaches 250%, and specific conductivity reaches 3.72ms/cm, septum body resistance 3.2 Ω, electrochemical stability window 4.7V, and barrier film intensity (transverse tensile strength 27MPa, longitudinal tensile strength 116MPa) meets battery assembling demand.
Embodiment 5
The present embodiment comprises the following steps:
(1) preparation of polymer nano granules: nanometer polymethylmethacrylate polyethylene being made median size 60nm by emulsion polymerization;
(2) preparation of film-casting liquid: take 1.00g polyvinylidene difluoride (PVDF) (PVDF), 1.00g polyvinylidene difluoride (PVDF)-R 1216 (PVDF-HFP), 0.1g nano silicon (median size is 100nm), 17.00g N-N,N-DIMETHYLACETAMIDE (DMAc) in 100ml Erlenmeyer flask, after stirring, add 0.30g nanometer polymethylmethacrylate, in 40 DEG C of stirred in water bath heating 5h, obtain film-casting liquid;
(3) shaping: step (2) gained film-casting liquid curtain coating on smooth glass plate is become blank film, casting temperature 50 DEG C, film thickness is 100 microns, leave standstill 1h;
(4) aftertreatment: immerse in dehydrated alcohol and realize being separated obtaining barrier film, then barrier film is placed in 60 DEG C of vacuum drying ovens and dries 5h.
The pick up of gained barrier film reaches 200%, and specific conductivity reaches 3.3 ms/cm, septum body resistance 4 Ω, electrochemical stability window 4.7V, and barrier film intensity (transverse tensile strength 30MPa, longitudinal tensile strength 120MPa) meets battery assembling demand.
Comparative example
Take 2.00g polyvinylidene difluoride (PVDF) (PVDF), 18.00g N-N,N-DIMETHYLACETAMIDE (DMAc) in 100ml Erlenmeyer flask, in 40 DEG C of stirred in water bath heating 5h, obtain film-casting liquid, then on smooth glass plate, curtain coating becomes blank film, film thickness is 100 microns, be immersed in the water realization after 1h to be separated and to obtain barrier film, then barrier film be placed in 60 DEG C of vacuum drying ovens and dry 5h.
The pick up of gained barrier film reaches 120%, and specific conductivity reaches 2.2ms/cm, septum body resistance 4.4 Ω, electrochemical stability window 4.65V, and barrier film intensity (transverse tensile strength 15MPa, longitudinal tensile strength 87MPa) meets battery assembling demand.
Claims (7)
1. a preparation method for lithium ion battery separator, is characterized in that, comprises the following steps:
(1) preparation of polymer nano granules: the mixture of one or more in polyethylene, polystyrene, polymethylmethacrylate, polyacrylic acid, polyacrylic ester or polypropylene is made polymer nano granules by exchange of solvent method or emulsion polymerization, the particle diameter of described polymer nano granules is 10-500nm;
(2) preparation of film-casting liquid: the ratio of the mixture of one or more in polymer polyvinylidene fluoride, Mierocrystalline cellulose, non-woven fabrics, polyvinylidene difluoride (PVDF)-R 1216, polyacrylonitrile or polyvinyl alcohol and thinner 1:1-15 is in mass ratio mixed, then the polymer nano granules being equivalent to polymer weight 2-50% is added, in 30-50 DEG C of stirred in water bath heating 3-6h, obtain film-casting liquid;
(3) shaping: step (2) gained film-casting liquid curtain coating is become blank film, leave standstill 1-3h;
(4) aftertreatment: be immersed in the water or immerse in organic solvent-normal hexane, hexanaphthene, dehydrated alcohol, methyl alcohol, toluene or dimethylbenzene, removes the thinner in barrier film, vacuum-drying.
2. the preparation method of lithium ion battery separator according to claim 1, is characterized in that: in step (1), and the particle diameter of described polymer nano granules is 50-300nm.
3. the preparation method of lithium ion battery separator according to claim 1 and 2, is characterized in that: in step (2), the mass ratio 1:4-9 of mixture and thinner.
4. the preparation method of lithium ion battery separator according to claim 1 and 2, is characterized in that: in step (2), add the polymer nano granules being equivalent to polymer weight 10-30%.
5. the preparation method of lithium ion battery separator according to claim 1 and 2, is characterized in that: in step (2), and described thinner is the mixture of one or more in N-N,N-DIMETHYLACETAMIDE, dibutyl phthalate or N-Methyl pyrrolidone.
6. the preparation method of lithium ion battery separator according to claim 1 and 2, it is characterized in that: in step (2), before mixing, also be added with nano-silicon, nano silicon, nano aluminium oxide or nano-calcium carbonate, particle diameter is 20-200nm, and addition is the 0.05-5.0% of polymer weight.
7. the preparation method of lithium ion battery separator according to claim 1 and 2, is characterized in that: in step (3), and the matrix of film-casting liquid curtain coating is smooth glass plate or stainless steel plate, casting temperature 40-80 DEG C; The thickness of gained blank film is 10-100 μm.
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Families Citing this family (13)
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| CN104362278B (en) * | 2014-11-19 | 2017-03-22 | 苏州大学 | Compound lithium-ion battery diaphragm and preparation method thereof |
| CN105006539A (en) * | 2015-07-10 | 2015-10-28 | 长兴东方红包装有限公司 | Cellulose-composite polyethylene diaphragm for lithium ion battery and preparation method thereof |
| CN105070871B (en) * | 2015-09-11 | 2016-08-31 | 江西师范大学 | Compound many curved hole membrane material that crosslinked polystyrene microsphere is filled and its preparation method and application |
| CN105789524A (en) * | 2016-04-29 | 2016-07-20 | 宁德卓高新材料科技有限公司 | Preparation method of polyvinyl alcohol isolating membrane and isolating membrane prepared |
| CN106207048B (en) * | 2016-07-29 | 2020-02-21 | 上海交通大学 | Preparation method of porous diaphragm material of lithium-air battery |
| CN108075091B (en) * | 2016-11-18 | 2019-10-22 | 中国科学院金属研究所 | A kind of preparation method of functional porous polyvinylidene fluoride film used for all-vanadium redox flow battery |
| CN107221628B (en) * | 2017-06-19 | 2023-10-13 | 宁波柔创纳米科技有限公司 | Preparation method of lithium battery diaphragm, lithium battery diaphragm and lithium ion battery |
| CN111755647A (en) * | 2019-03-27 | 2020-10-09 | 中南大学 | Preparation method of lithium-air battery composite diaphragm |
| CN111916617A (en) * | 2019-05-10 | 2020-11-10 | 湖南农业大学 | Cellulose-based functionalized diaphragm and preparation method and application thereof |
| CN110165129A (en) * | 2019-05-28 | 2019-08-23 | 大连中比动力电池有限公司 | Anti-oxidant high puncture strength dry method diaphragm of one kind and its preparation method and application |
| CN111253679B (en) * | 2020-03-20 | 2021-08-31 | 清华大学 | Composite material and preparation method and application thereof |
| CN111584802A (en) * | 2020-04-29 | 2020-08-25 | 西安理工大学 | Aramid nanofiber composite lithium ion battery diaphragm and preparation method thereof |
| CN114024090A (en) * | 2021-10-27 | 2022-02-08 | 长园泽晖新能源材料研究院(珠海)有限公司 | Composite lithium ion battery diaphragm and preparation method thereof |
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