TWI824636B - Solid-state electrolyte film and solid-state battery - Google Patents
Solid-state electrolyte film and solid-state battery Download PDFInfo
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- TWI824636B TWI824636B TW111128350A TW111128350A TWI824636B TW I824636 B TWI824636 B TW I824636B TW 111128350 A TW111128350 A TW 111128350A TW 111128350 A TW111128350 A TW 111128350A TW I824636 B TWI824636 B TW I824636B
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- 239000003792 electrolyte Substances 0.000 title abstract description 7
- 229920000642 polymer Polymers 0.000 claims abstract description 126
- 239000002245 particle Substances 0.000 claims abstract description 52
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 25
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 25
- 239000007784 solid electrolyte Substances 0.000 claims description 183
- 229910052744 lithium Inorganic materials 0.000 claims description 18
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 17
- 239000002608 ionic liquid Substances 0.000 claims description 16
- 238000002844 melting Methods 0.000 claims description 10
- 230000008018 melting Effects 0.000 claims description 10
- 238000002425 crystallisation Methods 0.000 claims description 7
- 230000008025 crystallization Effects 0.000 claims description 7
- 229920001223 polyethylene glycol Polymers 0.000 claims description 7
- 239000000654 additive Substances 0.000 claims description 6
- 230000000996 additive effect Effects 0.000 claims description 6
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 claims description 6
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 6
- 239000002033 PVDF binder Substances 0.000 claims description 5
- 239000002202 Polyethylene glycol Substances 0.000 claims description 5
- 229920002125 Sokalan® Polymers 0.000 claims description 5
- 239000003112 inhibitor Substances 0.000 claims description 5
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims description 5
- 229910000664 lithium aluminum titanium phosphates (LATP) Inorganic materials 0.000 claims description 4
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 4
- 229920005569 poly(vinylidene fluoride-co-hexafluoropropylene) Polymers 0.000 claims description 4
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 4
- NRJJZXGPUXHHTC-UHFFFAOYSA-N [Li+].[O--].[O--].[O--].[O--].[Zr+4].[La+3] Chemical compound [Li+].[O--].[O--].[O--].[O--].[Zr+4].[La+3] NRJJZXGPUXHHTC-UHFFFAOYSA-N 0.000 claims description 3
- SZEFOBMPGYTUDO-UHFFFAOYSA-N [O-2].[Ta+5].[La+3].[Li+] Chemical compound [O-2].[Ta+5].[La+3].[Li+] SZEFOBMPGYTUDO-UHFFFAOYSA-N 0.000 claims description 3
- DGQGEJIVIMHONW-UHFFFAOYSA-N [O-2].[Ta+5].[Zr+4].[La+3].[Li+] Chemical compound [O-2].[Ta+5].[Zr+4].[La+3].[Li+] DGQGEJIVIMHONW-UHFFFAOYSA-N 0.000 claims description 3
- CVJYOKLQNGVTIS-UHFFFAOYSA-K aluminum;lithium;titanium(4+);phosphate Chemical compound [Li+].[Al+3].[Ti+4].[O-]P([O-])([O-])=O CVJYOKLQNGVTIS-UHFFFAOYSA-K 0.000 claims description 3
- CEMTZIYRXLSOGI-UHFFFAOYSA-N lithium lanthanum(3+) oxygen(2-) titanium(4+) Chemical compound [Li+].[O--].[O--].[O--].[O--].[Ti+4].[La+3] CEMTZIYRXLSOGI-UHFFFAOYSA-N 0.000 claims description 3
- 239000004584 polyacrylic acid Substances 0.000 claims description 3
- AOBIOSPNXBMOAT-UHFFFAOYSA-N 2-[2-(oxiran-2-ylmethoxy)ethoxymethyl]oxirane Chemical compound C1OC1COCCOCC1CO1 AOBIOSPNXBMOAT-UHFFFAOYSA-N 0.000 claims description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 125000001153 fluoro group Chemical group F* 0.000 claims description 2
- 238000005979 thermal decomposition reaction Methods 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims 1
- 239000010408 film Substances 0.000 description 110
- 239000000084 colloidal system Substances 0.000 description 19
- 238000000576 coating method Methods 0.000 description 16
- 239000011248 coating agent Substances 0.000 description 13
- 239000007774 positive electrode material Substances 0.000 description 13
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 12
- -1 nickel cobalt manganese aluminum Chemical compound 0.000 description 12
- 239000002904 solvent Substances 0.000 description 12
- 239000007773 negative electrode material Substances 0.000 description 11
- 239000007787 solid Substances 0.000 description 9
- 150000003949 imides Chemical class 0.000 description 8
- 150000002500 ions Chemical class 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 230000007547 defect Effects 0.000 description 5
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 4
- 229910010941 LiFSI Inorganic materials 0.000 description 4
- 239000010406 cathode material Substances 0.000 description 4
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000011244 liquid electrolyte Substances 0.000 description 3
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- YQFWGCSKGJMGHE-UHFFFAOYSA-N 1-methyl-1-propylpyrrolidin-1-ium Chemical compound CCC[N+]1(C)CCCC1 YQFWGCSKGJMGHE-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000005279 LLTO - Lithium Lanthanum Titanium Oxide Substances 0.000 description 1
- 229910000733 Li alloy Inorganic materials 0.000 description 1
- 229910009178 Li1.3Al0.3Ti1.7(PO4)3 Inorganic materials 0.000 description 1
- 229910013188 LiBOB Inorganic materials 0.000 description 1
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 1
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 1
- KSKVUKASNOQQFE-UHFFFAOYSA-N [O-]B(OS(F)(=O)=O)OS(F)(=O)=O.[Li+] Chemical compound [O-]B(OS(F)(=O)=O)OS(F)(=O)=O.[Li+] KSKVUKASNOQQFE-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- DKNRELLLVOYIIB-UHFFFAOYSA-N bis(trifluoromethylsulfonyl)azanide;1-methyl-1-propylpyrrolidin-1-ium Chemical compound CCC[N+]1(C)CCCC1.FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F DKNRELLLVOYIIB-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000003682 fluorination reaction Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- 239000001989 lithium alloy Substances 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- FRMOHNDAXZZWQI-UHFFFAOYSA-N lithium manganese(2+) nickel(2+) oxygen(2-) Chemical compound [O-2].[Mn+2].[Ni+2].[Li+] FRMOHNDAXZZWQI-UHFFFAOYSA-N 0.000 description 1
- ACFSQHQYDZIPRL-UHFFFAOYSA-N lithium;bis(1,1,2,2,2-pentafluoroethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)C(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)C(F)(F)F ACFSQHQYDZIPRL-UHFFFAOYSA-N 0.000 description 1
- SRFGYPCGVWVBTC-UHFFFAOYSA-N lithium;dihydrogen borate;oxalic acid Chemical compound [Li+].OB(O)[O-].OC(=O)C(O)=O SRFGYPCGVWVBTC-UHFFFAOYSA-N 0.000 description 1
- DVATZODUVBMYHN-UHFFFAOYSA-K lithium;iron(2+);manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[Fe+2].[O-]P([O-])([O-])=O DVATZODUVBMYHN-UHFFFAOYSA-K 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000003223 protective agent Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical class OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
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Abstract
Description
本揭露內容是有關於一種固態電解質薄膜及包括所述固態電解質薄膜的固態電池。The present disclosure relates to a solid electrolyte film and a solid-state battery including the solid electrolyte film.
隨著科技的日新月異，各式各樣的可攜式電池逐漸問世，人們對於可攜式電池的高性能及輕量化等需求亦越來越高。隨著這些需求日益強烈，鋰離子型電池基於其能量密度高且能夠迅速充電等特點而得到人們的高度關注及廣泛使用。對於鋰離子型電池而言，常使用液態電解質來作為電池的導電材料，但液態電解質具有液漏的危險或者缺少長時間的穩定性的缺點以及易腐蝕、易燃燒、安全性差與可靠性低等問題，無法滿足安全性方面的要求。With the rapid development of technology, various portable batteries have gradually come out, and people's demand for high performance and lightweight of portable batteries is also increasing. As these demands become increasingly strong, lithium-ion batteries have attracted great attention and are widely used due to their high energy density and rapid charging capabilities. For lithium-ion batteries, liquid electrolytes are often used as the conductive material of the battery. However, liquid electrolytes have the disadvantages of leakage or lack of long-term stability, and are prone to corrosion, combustion, poor safety and low reliability. problem and cannot meet security requirements.
有鑑於此，固態電解質逐漸取代較為危險的液態電解質。然而，固態電解質仍存在著許多問題，例如，固態電解質在室溫條件下的離子電導率不高、固態電解質與正負電極之間介面阻抗較大等問題。因此，如何有效改善固態電解質的上述缺點，實為目前業界研發的重點。In view of this, solid electrolytes are gradually replacing more dangerous liquid electrolytes. However, there are still many problems with solid electrolytes, such as low ionic conductivity of solid electrolytes at room temperature and large interfacial impedance between solid electrolytes and positive and negative electrodes. Therefore, how to effectively improve the above-mentioned shortcomings of solid electrolytes is currently the focus of research and development in the industry.
根據本揭露的一些實施方式，一種固態電解質薄膜包括第一鋰鹽、第一高分子、第二高分子及固態電解質。第一高分子的重量平均分子量介於60000g/mol至1800000g/mol之間。第二高分子具有顆粒狀。固態電解質具有顆粒狀，且固態電解質的粒徑(D50)介於50奈米至2微米之間。 According to some embodiments of the present disclosure, a solid electrolyte film includes a first lithium salt, a first polymer, a second polymer and a solid electrolyte. The weight average molecular weight of the first polymer is between 60,000g/mol and 1,800,000g/mol. The second polymer has a granular shape. The solid electrolyte has a granular shape, and the particle size (D50) of the solid electrolyte is between 50 nanometers and 2 microns.
在本揭露的一些實施方式中，第一鋰鹽、第一高分子、第二高分子以及固態電解質的重量比為16至25：26至34：5至20：10至40。 In some embodiments of the present disclosure, the weight ratio of the first lithium salt, the first polymer, the second polymer and the solid electrolyte is 16 to 25: 26 to 34: 5 to 20: 10 to 40.
在本揭露的一些實施方式中，第一高分子為含氟高分子。 In some embodiments of the present disclosure, the first polymer is a fluorine-containing polymer.
在本揭露的一些實施方式中，第一高分子的熔點介於160℃至175℃之間，且第一高分子的熱穩定溫度介於300℃至400℃之間。 In some embodiments of the present disclosure, the melting point of the first polymer is between 160°C and 175°C, and the thermal stability temperature of the first polymer is between 300°C and 400°C.
在本揭露的一些實施方式中，第一鋰鹽包括氟化鋰、雙氟磺醯亞胺鋰、雙三氟甲烷磺醯亞胺鋰、雙(全氟乙基磺醯亞胺)鋰、二草酸硼酸鋰或其組合。 In some embodiments of the present disclosure, the first lithium salt includes lithium fluoride, lithium bisfluorosulfonimide, lithium bistrifluoromethanesulfonimide, lithium bis(perfluoroethylsulfonimide), lithium bis(perfluoroethylsulfonimide), Lithium oxalate borate or combinations thereof.
在本揭露的一些實施方式中，第一高分子包括聚偏二氟乙烯、聚偏氟乙烯-六氟丙烯共聚物或其組合，且第二高分子包括聚丙烯酸、聚甲基丙烯酸甲酯、三氟化硼-***錯合物、聚乙二醇、聚乙二醇二縮水甘油醚或其組合。 In some embodiments of the present disclosure, the first polymer includes polyvinylidene fluoride, polyvinylidene fluoride-hexafluoropropylene copolymer, or a combination thereof, and the second polymer includes polyacrylic acid, polymethylmethacrylate, Boron trifluoride-diethyl ether complex, polyethylene glycol, polyethylene glycol diglycidyl ether or combinations thereof.
在本揭露的一些實施方式中，固態電解質包括鋰鑭鋯氧、鋰鑭鋯鉭氧、鋰鑭鈦氧、鋰鑭鉭氧、磷酸鈦鋰鋁或其組合。In some embodiments of the present disclosure, the solid electrolyte includes lithium lanthanum zirconium oxide, lithium lanthanum zirconium tantalum oxide, lithium lanthanum titanium oxide, lithium lanthanum tantalum oxide, lithium aluminum titanium phosphate, or combinations thereof.
在本揭露的一些實施方式中，第一高分子具有第一重量平均分子量、第二重量平均分子量及第三重量平均分子量，第一重量平均分子量介於800000 g/mol至1000000 g/mol之間，第二重量平均分子量介於1300000 g/mol至1500000 g/mol之間，且第三重量平均分子量介於60000 g/mol至200000 g/mol之間。In some embodiments of the present disclosure, the first polymer has a first weight average molecular weight, a second weight average molecular weight, and a third weight average molecular weight, and the first weight average molecular weight is between 800,000 g/mol and 1,000,000 g/mol. , the second weight average molecular weight is between 1,300,000 g/mol and 1,500,000 g/mol, and the third weight average molecular weight is between 60,000 g/mol and 200,000 g/mol.
在本揭露的一些實施方式中，具有第一重量平均分子量的第一高分子、具有第二重量平均分子量的第一高分子及具有第三重量平均分子量的第一高分子的重量比為6~10：1.5~3：1。In some embodiments of the present disclosure, the weight ratio of the first polymer with the first weight average molecular weight, the first polymer with the second weight average molecular weight, and the first polymer with the third weight average molecular weight is 6~ 10:1.5~3:1.
在本揭露的一些實施方式中，固態電解質具有第一粒徑(D50)、第二粒徑(D50)以及第三粒徑(D50)，第一粒徑(D50)介於0.8微米至1.4微米之間，第二粒徑(D50)介於0.25微米至0.5微米之間，且第三粒徑(D50)介於80奈米至150奈米之間。In some embodiments of the present disclosure, the solid electrolyte has a first particle size (D50), a second particle size (D50), and a third particle size (D50). The first particle size (D50) is between 0.8 microns and 1.4 microns. between, the second particle size (D50) is between 0.25 microns and 0.5 microns, and the third particle size (D50) is between 80 nanometers and 150 nanometers.
在本揭露的一些實施方式中，具有第一粒徑(D50)的固態電解質、具有第二粒徑(D50)的固態電解質以及具有第三粒徑(D50)的固態電解質的重量比為10~20：30~45：35~50。In some embodiments of the present disclosure, the weight ratio of the solid electrolyte with the first particle diameter (D50), the solid electrolyte with the second particle diameter (D50), and the solid electrolyte with the third particle diameter (D50) is 10~ 20:30~45:35~50.
根據本揭露的一些實施方式，一種固態電池包括前述固態電解質薄膜、正極及負極。固態電解質薄膜的厚度介於20微米至70微米之間。正極及負極分別設置於固態電解質薄膜的相對兩表面。According to some embodiments of the present disclosure, a solid-state battery includes the aforementioned solid electrolyte film, a positive electrode, and a negative electrode. The thickness of the solid electrolyte film ranges from 20 microns to 70 microns. The positive electrode and the negative electrode are respectively disposed on opposite surfaces of the solid electrolyte film.
在本揭露的一些實施方式中，固態電池更包括凝膠結構以及緩衝結構。凝膠結構設置於正極與固態電解質薄膜之間，且包括第二鋰鹽、第一高分子以及結晶抑制添加劑。緩衝結構設置於負極與固態電解質薄膜之間，其中緩衝結構係凝膠結構或者離子液體。In some embodiments of the present disclosure, the solid-state battery further includes a gel structure and a buffer structure. The gel structure is disposed between the positive electrode and the solid electrolyte film, and includes a second lithium salt, a first polymer and a crystallization inhibitor additive. The buffer structure is arranged between the negative electrode and the solid electrolyte film, wherein the buffer structure is a gel structure or an ionic liquid.
在本揭露的一些實施方式中，凝膠結構的厚度介於1微米至10微米之間，且離子液體在1平方公分之固態電解質薄膜上的體積介於10微升至40微升之間。In some embodiments of the present disclosure, the thickness of the gel structure ranges from 1 micron to 10 microns, and the volume of the ionic liquid on 1 square centimeter of the solid electrolyte film ranges from 10 microliters to 40 microliters.
根據本揭露上述實施方式，由於本揭露的固態電解質薄膜包括第一鋰鹽、第一高分子、第二高分子以及具有特定粒徑的固態電解質，因此固態電解質薄膜在室溫條件下可具有較高的離子電導率，進而提升固態電池整體的效能。另一方面，由於本揭露是直接將第一鋰鹽、第一高分子、第二高分子及固態電解質整合於單一膜片中以形成固態電解質薄膜，因此可大幅提升製程的便利性。According to the above embodiments of the present disclosure, since the solid electrolyte film of the present disclosure includes a first lithium salt, a first polymer, a second polymer and a solid electrolyte with a specific particle size, the solid electrolyte film can have a relatively high performance under room temperature conditions. High ionic conductivity, thereby improving the overall performance of solid-state batteries. On the other hand, since the present disclosure directly integrates the first lithium salt, the first polymer, the second polymer and the solid electrolyte into a single diaphragm to form a solid electrolyte film, the convenience of the manufacturing process can be greatly improved.
以下將以圖式揭露本揭露之複數個實施方式，為明確地說明起見，許多實務上的細節將在以下敘述中一併說明。然而，應瞭解到，這些實務上的細節不應用以限制本揭露。也就是說，在本揭露部分實施方式中，這些實務上的細節是非必要的，因此不應用以限制本揭露。此外，為簡化圖式起見，一些習知慣用的結構與元件在圖式中將以簡單示意的方式繪示之。另外，為了便於讀者觀看，圖式中各元件的尺寸並非依實際比例繪示。A plurality of implementation manners of the present disclosure will be disclosed below in figures. For the purpose of clear explanation, many practical details will be explained together in the following description. However, it should be understood that these practical details should not be used to limit the disclosure. That is to say, in some implementations of the disclosure, these practical details are not necessary and therefore should not be used to limit the disclosure. In addition, for the sake of simplifying the drawings, some commonly used structures and components will be illustrated in a simple schematic manner in the drawings. In addition, for the convenience of readers, the dimensions of each element in the drawings are not drawn according to actual proportions.
應當理解，諸如「下」或「底部」和「上」或「頂部」的相對術語可在本文中用於描述一個元件與另一元件的關係，如圖式中所示。應當理解，相對術語旨在包括除了圖中所示的方位之外的裝置的不同方位。舉例而言，若一附圖中的裝置翻轉，則被描述為在其他元件的「下」側的元件將被定向在其他元件的「上」側。因此，示例性術語「下」可以包括「下」和「上」的取向，取決於附圖的特定取向。類似地，若一個附圖中的裝置翻轉，則被描述為在其它元件「下」或「下方」的元件將被定向為在其它元件「上方」。因此，示例性術語「下」或「下面」可以包括上方和下方的取向。It will be understood that relative terms, such as "lower" or "bottom" and "upper" or "top" may be used herein to describe one element's relationship to another element as illustrated in the drawings. It will be understood that relative terms are intended to encompass different orientations of the device in addition to the orientation illustrated in the figures. For example, if the device in the figures is turned over, elements described as "below" other elements would then be oriented "above" the other elements. Thus, the exemplary term "lower" may include both "lower" and "upper" orientations, depending on the particular orientation of the drawing. Similarly, if the device in the figures is turned over, elements described as "below" or "beneath" other elements would then be oriented "above" the other elements. Thus, the exemplary terms "lower" or "lower" may include both upper and lower orientations.
本揭露內容提供一種固態電解質薄膜及包括所述固態電解質薄膜的固態電池。由於本揭露的固態電解質薄膜包括鋰鹽、兩種類型的高分子及具有特定粒徑的固態電解質，因此固態電解質薄膜可具有較高的離子電導率。此外，藉由使用離子電導能力與固態電解質薄膜相近的凝膠結構將電極(正/負極)與固態電解質薄膜緊密地結合，可使固態電解質薄膜與電極之間具有較低的介面阻抗，有利於離子在介面的傳導。如此一來，即便在室溫(例如，介於20℃至60℃之間的溫度範圍)的條件下，固態電解池仍可具有良好的效能。The present disclosure provides a solid electrolyte film and a solid-state battery including the solid electrolyte film. Since the solid electrolyte film of the present disclosure includes a lithium salt, two types of polymers and a solid electrolyte with a specific particle size, the solid electrolyte film can have high ionic conductivity. In addition, by using a gel structure with ionic conductivity similar to that of the solid electrolyte film to tightly combine the electrode (positive/negative electrode) with the solid electrolyte film, the interface impedance between the solid electrolyte film and the electrode can be lowered, which is beneficial to Ion conduction at the interface. In this way, the solid-state electrolytic cell can still have good performance even at room temperature (for example, a temperature range between 20°C and 60°C).
請參閱第1圖，其繪示根據本揭露一些實施方式的固態電池100的截面示意圖。本揭露的固態電池100包括負極、正極以及固態電解質薄膜130，其中負極可例如包含負極材料層110以及負極集電體140，而正極可例如包含正極材料層120以及正極集電體150。在一些實施方式中，負極可包括例如是石墨、介相碳微球、矽碳、矽氧碳、鋰金屬、鋰合金、鈦酸鋰(簡稱LTO)或其組合之負極材料S1的負極材料層110以及例如是銅箔的負極集電體140，而正極可包括例如是鎳鈷錳(簡稱NCM)、鎳鈷錳鋁(簡稱NCMA)、鈷酸鋰(簡稱LCO)、鋰鎳錳氧 (簡稱LNMO)、錳酸鋰(簡稱LMO)、鎳鈷鋁(簡稱NCA)、磷酸鐵鋰(LiFePO
4，簡稱LFP)、磷酸錳鐵鋰(簡稱LMFP)或其組合之正極材料S2的正極材料層120以及例如是鋁箔的正極集電體150。在一些實施方式中，負極及正極分別設置於固態電解質薄膜130的相對兩表面(例如，第一表面131及第二表面133)，詳細而言，負極材料層110及正極材料層120將固態電解質薄膜130夾置於其間，且負極集電體140及正極集電體150將負極材料層110、正極材料層120及固態電解質薄膜130夾置於其間。
Please refer to FIG. 1 , which illustrates a schematic cross-sectional view of a solid-
在一些實施方式中，固態電池100可進一步包括凝膠結構160以及緩衝結構170。凝膠結構160可設置於正極材料層120與固態電解質薄膜130之間，並且緩衝結構170可設置於負極材料層110與固態電解質薄膜130之間。在一些實施方式中，緩衝結構170係等同於凝膠結構160，亦即，凝膠結構160不僅可設置於正極材料層120與固態電解質薄膜130之間，還可設置於負極材料層110與固態電解質薄膜130之間。在其他實施方式中，緩衝結構170係離子液體(將於下文中進一步說明)。本揭露的固態電池100大致上的結構如前文及第1圖所示，在以下敘述中，將進一步針對固態電池100中固態電解質薄膜130、凝膠結構160及緩衝結構170的細節進行更詳細的說明。需說明的是，為清楚起見，第1圖將固態電池100繪示中的部分元件繪示成彼此分離，但在實際的固態電池100結構中，各元件為彼此緊密結合的。
In some embodiments, the solid-
在一些實施方式中，固態電解質薄膜130包括第一鋰鹽、第一高分子、第二高分子以及固態電解質，且第一鋰鹽、第一高分子、第二高分子及固態電解質彼此均勻地混合。具體而言，第一鋰鹽可例如是氟化鋰(LiF)、雙氟磺醯亞胺鋰(LiO4NS2F2，簡稱LiFSI)、雙三氟甲烷磺醯亞胺鋰(LiN(CF3SO2)2，簡稱LiTFSI)、雙(全氟乙基磺醯亞胺)鋰(Li(C2F5SO2)2N，簡稱LiBETI)、二草酸硼酸鋰(LiB(C2O4)2)，簡稱LiBOB)或其組合；第
一高分子可例如是聚偏二氟乙烯(polyvinylidene difluoride，簡稱PVDF)、聚偏氟乙烯-六氟丙烯共聚物(polyvinylidene fluoride-hexafluoropropylene copolymer，簡稱PVDF-HFP)或其組合；第二高分子例如是聚丙烯酸(poly(acrylic acid)，簡稱PAA)、聚甲基丙烯酸甲酯(poly(methyl methacrylate，簡稱PMMA)、三氟化硼-***錯合物(BF3．OEt2)、聚乙二醇二縮水甘油醚(diepoxy-poly(ethylene glycol)，簡稱DIEPEG)、聚乙二醇(polyethylene glycol，簡稱PEG)或其組合；而固態電解質可例如是鋰鑭鋯氧(例如Li7La3Zr2O12，簡稱LLZO)、鋰鑭鋯鉭氧(例如Li5.5La3Zr1.75Ta0.25O12，簡稱LLZTO)、鋰鑭鈦氧(例如La0.57Li0.29TiO3，簡稱LLTO)、鋰鑭鉭氧(例如Li0.35La0.57Ta0.8O3，簡稱LLTaO)、磷酸鈦鋰鋁(例如Li1.3Al0.3Ti1.7(PO4)3，簡稱LATP)或其組合。
In some embodiments, the
在一些實施方式中，可透過將第一高分子的重量平均分子量控制在一定的範圍內，以使固態電解質薄膜130具有較佳的韌性及抗機械性。具體而言，由於在固態電池100的工作期間，負極材料層110及正極材料層120會不斷地對固態電解質薄膜130進行擠壓，因此透過控制第一高分子的重量平均分子量，可使固態電解質薄膜130具有良好的韌性及抗機械性，進而避免因負極材料層110及正極材料層120的膨脹擠壓而影響固態電池100的循環及造成固態電池100短路。在一些實施方式中，第一高分子的重量平均分子量介於60000g/mole至1800000g/mole之間。詳細而言，若第一高分子的重量平均分子量小於60000g/mole，第一高分子的鏈結度差，導致其無法提供固態電解質薄膜130良好的韌性以及抗機械性；若第一高分子的重量平均分子量大於1800000g/mole，第一高分子黏度過高，不利於製程期間膠體(膠體可視為固態電解質薄膜130的前驅物)的塗佈，進而影響固態電解質薄膜130的良率。在較佳的實施方式中，第一高分子的重量平均分子量可介於80000g/mole至1300000g/mole之間，以較佳地實現上述功效。In some embodiments, the
在一些實施方式中，第一高分子包括三種不同分子量的高分子。詳細而言，第一高分子具有第一重量平均分子量、第二重量平均分子量以及第三重量平均分子量，其中第一重量平均分子量介於800000 g/mol至1000000 g/mol之間，第二重量平均分子量介於1300000 g/mol至1500000 g/mol之間，而第三重量平均分子量介於60000 g/mol至200000 g/mol之間。具有第一重量平均分子量的第一高分子可用於作為成膜的主要試劑，在成型後可成為固態電解質薄膜130的主架構，其在膠體狀態下的黏度適合塗膜製程，有利於固態電解質薄膜130成型。具有第二重量平均分子量的第一高分子可助於提升固態電解質薄膜130的機械強度(例如，延伸性及應力)。具有第三重量平均分子量的第一高分子可作為固態電解質的分散劑和保護劑，使固態電解質完整且均勻地分散於固態電解質薄膜130中。若欲提高固態電解質薄膜130的機械強度，比起僅使用小於等於1000000 g/mol之重量平均分子量的高分子作為第一高分子，同時使用具有第二重量平均分子量的第一高分子可以得到較佳的機械強度；僅使用1300000 g/mol至1500000 g/mol之重量平均分子量的高分子作為第一高分子，則膠體塗佈較為困難，成膜厚度與狀況不易控制。整體而言，透過使第一高分子包括三種不同分子量的高分子，可使固態電解質薄膜130利於成膜並且具有穩定的主架構，並可使固態電解質薄膜130具有優異的機械強度，又同時使固態電解質完整且均勻地分散於固態電解質薄膜130中。在一些具體實例中，具有第一重量平均分子量範圍的第一高分子、第二重量平均分子量的第一高分子以及具有第三重量平均分子量的第一高分子的重量比為6~10：1.5~3：1，以利於實現上述功效。In some embodiments, the first polymer includes three polymers of different molecular weights. In detail, the first polymer has a first weight average molecular weight, a second weight average molecular weight and a third weight average molecular weight, wherein the first weight average molecular weight is between 800000 g/mol and 1000000 g/mol, and the second weight average molecular weight is between 800000 g/mol and 1000000 g/mol. The average molecular weight ranges from 1,300,000 g/mol to 1,500,000 g/mol, while the third weight average molecular weight ranges from 60,000 g/mol to 200,000 g/mol. The first polymer with the first weight average molecular weight can be used as the main reagent for film formation, and can become the main structure of the
在一些實施方式中，可透過將第一高分子的熔點控制在一定的範圍內，以使固態電解質薄膜130具有較佳的性能。具體而言，在固態電解質薄膜130成型期間，溶劑(溶劑可例如是4-二甲氨基吡啶、二甲基甲醯胺、二甲基甲醯胺或其組合，必要時可摻雜少量甲苯以提升揮發性)可透過烘烤製程離開膠體，使得膠體逐漸成膜，為避免溶劑蒸散後所形成的微小孔洞或缺陷對固態電解質薄膜130的性能產生不利的影響(例如，產生縱向貫穿固態電解質薄膜130的孔洞或缺陷，使得固態電池100發生微短路)，在烘烤製程期間可先將位於膠體之表面的溶劑完全地去除(此步驟為第一階段)後，再逐漸升溫以使膠體中的高分子(例如，第一高分子)接近其玻璃轉換溫度(glass transition temperature，Tg)而達到部分熔融的狀態(此步驟為第二階段)，進而開始流動以填補因溶劑蒸散所產生的孔洞或缺陷。基於上述，透過控制第一高分子的熔點，可使第一高分子在第一階段維持固態，並在第二階段達到部分熔融的狀態，以避免成膜後的固態電解質薄膜130發生微短路等的電性問題，進而提升固態電解質薄膜130的電性功能。在一些實施方式中，第一高分子的熔點可介於160℃至175℃之間。詳細而言，若第一高分子的熔點小於160℃，第一高分子可能在第一階段即達到熔融的狀態，進而干擾溶劑的去除；而若第一高分子的熔點大於175℃，第一高分子則可能無法在第二階段順利地達到熔融的狀態，導致固態電解質薄膜130中的孔洞或缺陷過多，進而影響固態電池100的電性功能。在較佳的實施方式中，第一高分子的熔點可介於160℃至165℃之間，以較佳地實現上述功效。另一方面，由於在固態電池100的工作期間會產生一定的熱能，因此將第一高分子的熔點控制在上述範圍可避免第一高分子在固態電池100的工作期間熔化以造成短路。在一些實施方式中，第一高分子的熱穩定溫度(例如，對第一高分子進行熱重分析時所得到的熱分解溫度)可介於300℃至400℃之間，以具有良好的穩定度，進而使得固態電池100在工作期間具有良好的熱穩定性。在一些實施方式中，第一高分子的的結晶點(crystallizing point)介於120℃至140℃之間(較佳為介於120℃至130℃之間)，以具備良好的成膜性。In some embodiments, the
在一些實施方式中，第二高分子具有顆粒狀，以適度地破壞第一高分子所形成之薄膜的連續延伸狀態。具體而言，由於第一高分子為成膜性佳的微小非顆粒材料，因此當第一高分子單獨地存在時，其容易形成連續延伸的薄膜，而當將第二高分子摻雜於第一高分子中時，基於顆粒狀的第二高分子可適度地破壞(調整)第一高分子之間的連結，使固態電解質薄膜130產生適量的孔紋，進而提升離子的穿透性，使得離子的電導率提升。在一些實施方式中，可進一步透過第一高分子及第二高分子的比例關係來較佳地實現上述功效。具體而言，第一高分子以及第二高分子的重量比可控制在16~25：26~34的範圍內。In some embodiments, the second polymer has a granular shape to moderately disrupt the continuous extension state of the film formed by the first polymer. Specifically, since the first polymer is a tiny non-granular material with good film-forming properties, when the first polymer exists alone, it can easily form a continuously extending film, and when the second polymer is doped with the third When contained in a polymer, the granular second polymer can moderately destroy (adjust) the connections between the first polymers, causing the
在一些實施方式中，固態電解質具有顆粒狀，且固態電解質的粒徑(D50)介於50奈米至2微米之間，以提升固態電解質薄膜130的電性功能。更具體而言，當固態電解質的粒徑落在上述範圍中時，其顆粒尺寸小且尺寸均一，如此可避免大尺寸之固態電解質所造成之固態電解質薄膜130表面凹凸不平的情形發生，進而使固態電解質薄膜130與其相鄰的層別(例如，凝膠結構160及緩衝結構170)緊密且充分地咬合，以避免空氣存在於固態電解質薄膜130與相鄰的層別之間，進而避免短路或性能不良的情況發生。此外，固態電解質的顆粒尺寸小且尺寸均一還可促使固態電解質均勻地分散於固態電解質薄膜130中，以避免固態電解質薄膜130表面凹凸不平的情形發生。基於上述，由於固態電解質薄膜130表面凹凸不平的情形不會發生，因此可避免固態電解質薄膜130因應力不均而導致性能較不佳。另一方面，由於在相同的質量下，顆粒小之固態電解質的數目總和大於顆粒大之固態電解質的數目總和，因此小顆粒之固態電解質所形成的可穿梭通道多於大顆粒之固態電解質所造成的可穿梭通道，故顆粒小的固態電解質可提供較優異的傳導能力，進而提升固態電池100的離子的電導率。值得說明的是，一般而言，當固態電解質的粒徑越小，其所能夠產生的晶界表面積及接觸面積會越大，但粒徑小之固態電解質亦容易在塗佈過程中反應過於劇烈，導致不必要的副反應發生，因此在較佳的實施方式中，固態電解質的粒徑可小於500奈米(例如，介於50奈米至300奈米之間)，以較佳地兼顧塗佈時的勻漿性及塗佈後的導電性需求。In some embodiments, the solid electrolyte has a granular shape, and the particle size (D50) of the solid electrolyte is between 50 nanometers and 2 microns to improve the electrical function of the
在一些實施方式中，固態電解質包括三種不同的粒徑(D50)範圍。詳細而言，固態電解質具有第一粒徑(D50)、第二粒徑(D50)及第三粒徑(D50)，其中第一粒徑介於0.8微米至1.4微米之間，第二粒徑介於0.25微米至0.5微米之間，而第三粒徑介於80奈米至150奈米之間。具體而言，如前所述，當粒徑小之固態電解質的數量越多，代表單位體積內的可穿梭通道數目較多，然而粒徑小之固態電解質亦容易在塗佈過程中反應過於劇烈而鋰氟化，導致膠體難以塗佈成膜，進而影響固態電解質薄膜130的厚度。因此，在考量上述反應性問題後，可以選擇以粒徑較大(即，具有第一、第二粒徑)的固態電解質來取代部分粒徑較小(即，具有第三粒徑)的固態電解質，來使固態電解質薄膜130的成膜性更為順利，並且透過混合不同粒徑的固態電解質，可使最終形成的固態電解質薄膜130具有較強的結構強度。整體而言，藉由上述三種不同粒徑之固態電解質的配置，固態電解質薄膜130可具有較佳的成膜性以及較強的結構強度。在一些實施方式中，具有第一粒徑的固態電解質、具有第二粒徑的固態電解質及具有第三粒徑的固態電解質的重量比為10~20：30~45：35~50，以利於實現上述功效。In some embodiments, the solid electrolyte includes three different particle size (D50) ranges. In detail, the solid electrolyte has a first particle size (D50), a second particle size (D50) and a third particle size (D50), wherein the first particle size is between 0.8 microns and 1.4 microns, and the second particle size is between 0.8 microns and 1.4 microns. Between 0.25 microns and 0.5 microns, and the third particle size ranges between 80 nanometers and 150 nanometers. Specifically, as mentioned above, when the number of solid electrolytes with small particle sizes is greater, it means that the number of shuttle channels per unit volume is larger. However, solid electrolytes with small particle sizes are also prone to react too violently during the coating process. However, lithium fluorination makes it difficult for the colloid to be coated and formed into a film, thereby affecting the thickness of the
基於上述，本揭露的固態電解質薄膜130可包括第一鋰鹽、第一高分子、第二高分子及固態電解質，且第一鋰鹽、第一高分子、第二高分子及固態電解質的重量比為16~25：26~34：5~20：10~40，以使固態電解質薄膜130具有較佳的均勻度，進而具有較佳的離子穿透率及電導率。在一些實施方式中，固態電解質薄膜130的厚度H1可介於10微米至100微米之間，以兼具良好的耐受性與韌性以及合適的能量密度。詳細而言，當固態電解質薄膜130的厚度H1小於10微米時，易導致固態電解質薄膜130受撕裂或刺穿；當固態電解質薄膜130的厚度H1大於100微米時，易導致固態電解質薄膜130的能量密度不足。在較佳的實施方式中，固態電解質薄膜130的厚度H1可介於20微米至70微米之間，以較佳地實現上述功效。Based on the above, the
在一些實施方式中，凝膠結構160可包括第二鋰鹽、前文所述的第一高分子以及結晶抑制添加劑。具體而言，第二鋰鹽可例如是雙氟磺醯亞胺鋰(LiO4NS2F2，簡稱LiFSI)、雙三氟甲烷磺醯亞胺鋰(LiN(CF3SO2)2，簡稱LiTFSI)、lithium(fluorosulfonyl)((3-(1-methyl-1H-imidazol-3-ium-3-yl)propyl)sulfonyl)imide)(簡稱LiFSMIPTFSI)、N,N-Bis(trifluoromethylsulfony aniline)或其組合；第一高分子可例如是前文所述的聚偏二氟乙烯、聚偏氟乙烯-六氟丙烯共聚物或其組合；合適的結晶抑制添加劑可例如是丙烯酸酯類聚合物，諸如聚丙烯酸丁酯、聚丙烯酸乙基己酯或聚甲基丙烯酸甲酯；三氧化二鋁；二氧化矽或其組合。凝膠結構160中存在結晶抑制添加劑可以調整第一高分子之結晶狀況，提高離子電導率。由於凝膠結構160可設置於電極(正極/負極)與固態電解質薄膜130之間，因此可避免電極與固態電解質薄膜130之間因空氣的存在而影響固態電池100的離子電導率，並可降低電極與固態電解質薄膜130之間的介面阻抗。此外，當固態電解質薄膜130仍存在少量的凹凸點時，凝膠結構160還可配置以與具有凹凸不平之表面的固態電解質薄膜130緊密地咬合，以使固態電解質薄膜130能夠透過凝膠結構160緊密地與電極結合。另一方面，由於凝膠結構160的配方與
固態電解質薄膜130的配方相近(例如，凝膠結構160與固態電解質薄膜130皆包括鋰鹽以及第一高分子)，因此凝膠結構160與固態電解質薄膜130的相容性高，有助於提升固態電池100的電性功能。在一些實施方式中，第二鋰鹽、第一高分子以及結晶抑制添加劑的重量比落在15~30：30~40：5~15的範圍內，進而確保凝膠結構160的固含量低於固態電解質薄膜130的固含量。在一些實施方式中，凝膠結構160的厚度H2介於1微米至10微米之間，以兼具良好的耐受性與韌性及合適的能量密度。詳細而言，當凝膠結構160的厚度H2小於1微米時，易導致凝膠結構160受撕裂或刺穿；當凝膠結構160的厚度H2大於10微米時，則易導致凝膠結構160的能量密度不足。在較佳的實施方式中，凝膠結構160的厚度H2可介於3微米至5微米之間，以較佳地實現上述功效。
In some embodiments, the
在一些實施方式中，當緩衝結構170係離子液體時，離子液體可例如是N-甲基-N-丙基吡咯啶雙(三氟甲烷磺醯)亞胺鹽(N-methyl-N-propylpyrrolidiniumbis(trifluoromethanesulfonyl)imide，簡稱[pyr13][Ntf2])、溶於二乙基吡咯啶雙(氟磺醯)亞胺鹽的雙氟磺醯亞胺鋰(LiO4NS2F2 dissolved in diethylpyrrolidiniumbis(fluorosulfonyl)imide，簡稱Li[FSI]in[C2epyr][FSI])、二氟草酸硼酸鋰(C2BF2LiO4，簡稱LiDFOB)、雙氟磺醯亞胺鋰/N-甲基-N-丙基吡咯啶雙氟磺醯亞胺鹽(LiO
4NS
2F
2/C
8H
18F
2N
2O
4S
2，簡稱LiFSI/PMPFSI)、雙三氟甲烷磺醯亞胺鋰/N-甲基-N-丙基吡咯啶雙氟磺醯亞胺鹽(LiN(CF
3SO
2)
2/C
8H
18F
2N
2O
4S
2，簡稱LiTFSI/PMPFSI)或上述任意的組合。離子液體可有效提升離子的電導率，且僅需少量的離子液體便可達到良好的離子傳導效益，並可降低負極材料層110與固態電解質薄膜130之間的介面阻抗。在一些實施方式中，離子液體在1平方公分之固態電解質薄膜130上的體積介於10微升至40微升之間。詳細而言，若離子液體的體積小於10微升，可能導致離子傳遞效率過低或導致低溫性能衰敗；若離子液體的體積大於40微升，可能導致能量密度過低。另一方面，由於離子液體耐低/高溫(例如，可承受-95℃至400℃的溫度)，因此可維持固態電池100在工作期間的安全性。
In some embodiments, when the
應瞭解到，已敘述過的元件連接關係與功效將不再重複贅述，合先敘明。在以下敘述中，將簡單說明固態電池100的製備方法。It should be understood that the connection relationships and functions of the components that have been described will not be repeated and will be explained first. In the following description, the method of manufacturing the solid-
首先，將溶劑(溶劑可例如是4-二甲氨基吡啶、二甲基甲醯胺、二甲基甲醯胺或其組合，必要時可摻雜少量甲苯)、第一高分子、第二高分子、第一鋰鹽及固態電解質依序置入行星式攪拌器中進行攪拌混合以形成混合物，並以黏度計監測攪拌期間混合物的黏度變化，以將混合物的黏度控制在介於3000cps至5000cps之間，進而確保後續所形成的膠體是利於塗佈的。詳細而言，當上述混合物的黏度小於3000cps時，易導致膠體因流動性過高而不利於塗佈；當上述混合物的黏度大於5000cps時，易導致膠體因流動性過低而難以分散成膜。在一些實施方式中，公轉速度可例如是60rpm±50%，自轉速度可例如是3500rpm±10%，並且攪拌時間可介於2小時至5小時之間。在充分地攪拌混合之後，便可得到膠體，且第一高分子、第二高分子、第一鋰鹽、固態電解質溶劑均勻地分佈於膠體中。First, the solvent (the solvent can be, for example, 4-dimethylaminopyridine, dimethylformamide, dimethylformamide or a combination thereof, and a small amount of toluene can be added if necessary), the first polymer, the second high molecular weight The molecules, the first lithium salt and the solid electrolyte are sequentially placed in a planetary stirrer for stirring and mixing to form a mixture, and a viscometer is used to monitor the viscosity change of the mixture during the stirring to control the viscosity of the mixture between 3000cps and 5000cps. time to ensure that the subsequent colloid formed is conducive to coating. Specifically, when the viscosity of the above mixture is less than 3000 cps, the colloid may have too high fluidity and is not conducive to coating; when the viscosity of the above mixture is greater than 5000 cps, the colloid may have too low fluidity and is difficult to disperse into a film. In some embodiments, the revolution speed may be, for example, 60 rpm ± 50%, the rotation speed may be, for example, 3500 rpm ± 10%, and the stirring time may be between 2 hours and 5 hours. After sufficient stirring and mixing, a colloid can be obtained, and the first polymer, the second polymer, the first lithium salt, and the solid electrolyte solvent are evenly distributed in the colloid.
隨後，將膠體脫泡，並將脫泡後的膠體導入間歇式塗佈設備進行塗佈。在一些實施方式中，塗佈期間所使用的刮刀為間隔(gap)式刮刀。在一些實施方式中，塗佈設備先以0.4公尺/分鐘至0.8公尺/分鐘的速度進行30秒至90秒的塗佈，以確認刮刀內側多餘膠體已往回溢流，再以0.2公尺/分鐘至0.4公尺/分鐘的速度進行塗佈至膠體耗盡。接著，以5公尺至15公尺的烘烤距離及100℃至130℃的溫度在例如是烤箱的設備中對塗佈後的膠體進行表面乾處理，隨後再以125℃至135℃的溫度在例如是加熱板的單方向加熱之烘烤設備中對塗佈後的膠體進行歷時0.5小時至1小時的深層乾處理。在進行上述步驟後，便完成第一道烘烤製程。Subsequently, the colloid is degassed, and the degassed colloid is introduced into intermittent coating equipment for coating. In some embodiments, the doctor blade used during coating is a gap doctor blade. In some embodiments, the coating equipment first performs coating at a speed of 0.4 m/min to 0.8 m/min for 30 seconds to 90 seconds to confirm that the excess colloid on the inside of the scraper has overflowed back, and then at a speed of 0.2 m/min. /min to 0.4 m/min until the colloid is exhausted. Then, the coated colloid is surface-dried in a device such as an oven with a baking distance of 5 meters to 15 meters and a temperature of 100°C to 130°C, and then the surface is dried at a temperature of 125°C to 135°C. The coated colloid is subjected to deep drying treatment for 0.5 to 1 hour in a baking device with unidirectional heating such as a heating plate. After performing the above steps, the first baking process is completed.
隨後，將完成第一道烘烤製程後的膜片置入例如是烘箱的設備中，以進行第二道烘烤製程。在一些實施方式中，第二道烘烤製程可包括第一階段以及第二階段，其中第一階段的烘烤溫度介於80℃至100℃之間，且烘烤時間介於0.5小時至1小時之間，而第二階段的烘烤溫度介於160℃至180℃之間，且烘烤時間介於0.5小時至1小時之間。如前文所述，第一階段的烘烤可先將位於膜片之表面的溶劑完全地去除，而第二階段的烘烤可使膜片中的高分子接近其玻璃轉換溫度而達到部分熔融的狀態，進而開始流動以填補因溶劑蒸散所產生的孔洞或缺陷，以藉此提升固態電解質薄膜130的結構完整性。在進行上述步驟之後，便可得到本揭露的固態電解質薄膜130。Subsequently, the diaphragm that has completed the first baking process is placed in a device such as an oven to perform the second baking process. In some embodiments, the second baking process may include a first stage and a second stage, wherein the baking temperature in the first stage is between 80°C and 100°C, and the baking time is between 0.5 hours and 1 hour. hours, while the baking temperature in the second stage is between 160°C and 180°C, and the baking time is between 0.5 hours and 1 hour. As mentioned above, the first stage of baking can completely remove the solvent on the surface of the diaphragm, while the second stage of baking can bring the polymer in the diaphragm close to its glass transition temperature and reach a partially molten state. state, and then begins to flow to fill the holes or defects caused by the evaporation of the solvent, thereby improving the structural integrity of the
接著，以塗佈的方式在正極材料層120背對於正極集電體150的表面形成凝膠結構160，並接著將固態電解質薄膜130黏附於凝膠結構160背對於正極材料層120的表面，再接著於室溫的條件下靜置0.5小時至1.5小時後，置入真空乾燥箱進行烘乾，以得到半極片(半極片包括正極材料層120、正極集電體150以及固態電解質薄膜130)。隨後，將緩衝結構170形成於固態電解質薄膜130背對於凝膠結構160的表面。詳細而言，若緩衝結構170為凝膠結構160，是以塗佈的方式形成；若緩衝結構170為離子液體，則是以滴液的方式形成，並待離子液體充分滲入至固態電解質薄膜130之後，再將已設置於負極集電體140上的負極材料層110透過緩衝結構170(凝膠結構160或離子液體)壓合於固態電解質薄膜130上，並再置入真空乾燥箱進行烘乾，進而得到本揭露的固態電池100。Next, a
根據本揭露上述實施方式，由於本揭露的固態電解質薄膜包括第一鋰鹽、第一高分子、第二高分子以及具有特定粒徑的固態電解質，因此固態電解質薄膜在室溫條件下可具有較高的離子電導率，進而提升固態電池整體的效能。此外，緩衝結構及凝膠結構的配置可有助於降低固態電解質薄膜與正極材料層及負極材料層之間的介面阻抗並且提升離子電導率，進而提升固態電池整體的效能。另一方面，由於第一高分子可進一步包括三種不同分子量的高分子，且固態電解質可進一步具有三種不同的粒徑(D50)，因此可有利於固態電解質薄膜成膜並且具有穩定的主架構，並可使固態電解質薄膜具有優異的機械強度，同時使固態電解質可完整且均勻地分散於固態電解質薄膜中。此外，由於本揭露是直接將第一鋰鹽、第一高分子、第二高分子及固態電解質整合於單一膜片中以形成固態電解質薄膜，因此可大幅提升製程的便利性。According to the above embodiments of the present disclosure, since the solid electrolyte film of the present disclosure includes a first lithium salt, a first polymer, a second polymer and a solid electrolyte with a specific particle size, the solid electrolyte film can have a relatively high performance under room temperature conditions. High ionic conductivity, thereby improving the overall performance of solid-state batteries. In addition, the configuration of the buffer structure and the gel structure can help reduce the interface resistance between the solid electrolyte film and the positive and negative electrode material layers and increase the ionic conductivity, thereby improving the overall performance of the solid-state battery. On the other hand, since the first polymer may further include polymers with three different molecular weights, and the solid electrolyte may further have three different particle sizes (D50), it may be beneficial to film formation of the solid electrolyte film and have a stable main structure, The solid electrolyte film can have excellent mechanical strength, and at the same time, the solid electrolyte can be completely and evenly dispersed in the solid electrolyte film. In addition, since the present disclosure directly integrates the first lithium salt, the first polymer, the second polymer and the solid electrolyte into a single diaphragm to form a solid electrolyte film, the convenience of the manufacturing process can be greatly improved.
雖然本揭露已以實施方式揭露如上，然其並非用以限定本揭露，任何熟習此技藝者，在不脫離本揭露之精神和範圍內，當可作各種之更動與潤飾，因此本揭露之保護範圍當視後附之申請專利範圍所界定者為準。Although the disclosure has been disclosed in the above embodiments, it is not intended to limit the disclosure. Anyone skilled in the art can make various changes and modifications without departing from the spirit and scope of the disclosure. Therefore, the protection of the disclosure The scope shall be determined by the appended patent application scope.
100:固態電池 110:負極材料層100:Solid state battery 110: Negative material layer
111:表面 111:Surface
120:正極材料層 120: positive electrode material layer
121:表面 121:Surface
130:固態電解質薄膜 130:Solid electrolyte film
131:第一表面 131: First surface
133:第二表面 133: Second surface
140:負極集電體 140: Negative current collector
150:正極集電體 150:Positive current collector
160:凝膠結構 160: Gel structure
170:緩衝結構 170:Buffer structure
H1,H2:厚度 H1, H2: Thickness
S1:負極材料 S1: negative electrode material
S2:正極材料 S2: positive electrode material
為讓本揭露之上述和其他目的、特徵、優點與實施例能更明顯易懂，所附圖式之說明如下： 第1圖繪示根據本揭露一些實施方式的固態電池的截面示意圖。 In order to make the above and other objects, features, advantages and embodiments of the present disclosure more obvious and understandable, the accompanying drawings are described as follows: Figure 1 illustrates a schematic cross-sectional view of a solid-state battery according to some embodiments of the present disclosure.
100:固態電池 100:Solid state battery
110:負極材料層 110: Negative material layer
111:表面 111:Surface
120:正極材料層 120: positive electrode material layer
121:表面 121:Surface
130:固態電解質薄膜 130:Solid electrolyte film
131:第一表面 131: First surface
133:第二表面 133: Second surface
140:負極集電體 140: Negative current collector
150:正極集電體 150:Positive current collector
160:凝膠結構 160:Gel structure
170:緩衝結構 170:Buffer structure
H1,H2:厚度 H1, H2: Thickness
S1:負極材料 S1: negative electrode material
S2:正極材料 S2: positive electrode material
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| US17/896,610 US20230163354A1 (en) | 2021-09-03 | 2022-08-26 | Solid-state electrolyte film and solid-state battery |
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| CN105098234A (en) * | 2015-09-22 | 2015-11-25 | 中国科学院物理研究所 | Solid electrolyte material, and electrolyte layer and lithium ion battery comprising solid electrolyte material |
| CN111234240A (en) * | 2020-01-15 | 2020-06-05 | 南方科技大学 | Polycaprolactone-based hyperbranched polymer all-solid-state electrolyte and lithium ion battery |
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| CN111234240A (en) * | 2020-01-15 | 2020-06-05 | 南方科技大学 | Polycaprolactone-based hyperbranched polymer all-solid-state electrolyte and lithium ion battery |
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