JP6281808B2 - 二次電池 - Google Patents
二次電池 Download PDFInfo
- Publication number
- JP6281808B2 JP6281808B2 JP2013209155A JP2013209155A JP6281808B2 JP 6281808 B2 JP6281808 B2 JP 6281808B2 JP 2013209155 A JP2013209155 A JP 2013209155A JP 2013209155 A JP2013209155 A JP 2013209155A JP 6281808 B2 JP6281808 B2 JP 6281808B2
- Authority
- JP
- Japan
- Prior art keywords
- lithium
- negative electrode
- secondary battery
- ether
- ionic liquid
- 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.)
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 135
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 68
- 239000008151 electrolyte solution Substances 0.000 claims description 60
- 229910052744 lithium Inorganic materials 0.000 claims description 53
- 239000002608 ionic liquid Substances 0.000 claims description 47
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 33
- 229910052799 carbon Inorganic materials 0.000 claims description 30
- 229910002804 graphite Inorganic materials 0.000 claims description 30
- 239000010439 graphite Substances 0.000 claims description 30
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 28
- 229910052760 oxygen Inorganic materials 0.000 claims description 28
- 239000001301 oxygen Substances 0.000 claims description 28
- 150000003839 salts Chemical class 0.000 claims description 28
- 229910052717 sulfur Inorganic materials 0.000 claims description 26
- 239000011593 sulfur Substances 0.000 claims description 26
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 24
- 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 24
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 22
- 229910018091 Li 2 S Inorganic materials 0.000 claims description 19
- 239000005077 polysulfide Substances 0.000 claims description 16
- 229920001021 polysulfide Polymers 0.000 claims description 16
- 150000008117 polysulfides Polymers 0.000 claims description 16
- 238000007599 discharging Methods 0.000 claims description 13
- 239000007773 negative electrode material Substances 0.000 claims description 12
- 239000007774 positive electrode material Substances 0.000 claims description 9
- GLNWILHOFOBOFD-UHFFFAOYSA-N lithium sulfide Chemical compound [Li+].[Li+].[S-2] GLNWILHOFOBOFD-UHFFFAOYSA-N 0.000 claims description 5
- 238000007614 solvation Methods 0.000 claims description 2
- ARNWQMJQALNBBV-UHFFFAOYSA-N lithium carbide Chemical compound [Li+].[Li+].[C-]#[C-] ARNWQMJQALNBBV-UHFFFAOYSA-N 0.000 claims 1
- 208000028659 discharge Diseases 0.000 description 47
- -1 that is Inorganic materials 0.000 description 43
- 239000002904 solvent Substances 0.000 description 39
- 229910052783 alkali metal Inorganic materials 0.000 description 33
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 19
- 239000003792 electrolyte Substances 0.000 description 19
- 229910001416 lithium ion Inorganic materials 0.000 description 15
- 239000013078 crystal Substances 0.000 description 14
- 150000001340 alkali metals Chemical class 0.000 description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 239000011149 active material Substances 0.000 description 12
- 238000012360 testing method Methods 0.000 description 12
- 150000002170 ethers Chemical class 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 10
- 230000007423 decrease Effects 0.000 description 10
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 9
- 239000011230 binding agent Substances 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 239000007772 electrode material Substances 0.000 description 7
- 238000002474 experimental method Methods 0.000 description 7
- 239000010410 layer Substances 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 125000000217 alkyl group Chemical group 0.000 description 6
- 239000006258 conductive agent Substances 0.000 description 6
- 125000005843 halogen group Chemical group 0.000 description 6
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- 238000007086 side reaction Methods 0.000 description 6
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- 239000000243 solution Substances 0.000 description 5
- 239000002033 PVDF binder Substances 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 description 4
- 229910001413 alkali metal ion Inorganic materials 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
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- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 description 4
- 230000004580 weight loss Effects 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 description 3
- 239000006230 acetylene black Substances 0.000 description 3
- 239000002388 carbon-based active material Substances 0.000 description 3
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- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 3
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 230000002427 irreversible effect Effects 0.000 description 3
- 239000003273 ketjen black Substances 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
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- 229920002451 polyvinyl alcohol Polymers 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 description 3
- 125000006306 4-iodophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1I 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- 229910001245 Sb alloy Inorganic materials 0.000 description 2
- 229910000676 Si alloy Inorganic materials 0.000 description 2
- 229910001128 Sn alloy Inorganic materials 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 2
- 150000004973 alkali metal peroxides Chemical class 0.000 description 2
- 239000002140 antimony alloy Substances 0.000 description 2
- 239000004760 aramid Substances 0.000 description 2
- 229920003235 aromatic polyamide Polymers 0.000 description 2
- 239000002134 carbon nanofiber Substances 0.000 description 2
- 239000002041 carbon nanotube Substances 0.000 description 2
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- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- TXLQIRALKZAWHN-UHFFFAOYSA-N dilithium carbanide Chemical compound [Li+].[Li+].[CH3-].[CH3-] TXLQIRALKZAWHN-UHFFFAOYSA-N 0.000 description 2
- 238000003411 electrode reaction Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 239000011245 gel electrolyte Substances 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 238000003780 insertion Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
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- 229910052976 metal sulfide Inorganic materials 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 150000002898 organic sulfur compounds Chemical class 0.000 description 2
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- 239000000047 product Substances 0.000 description 2
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- 125000006850 spacer group Chemical group 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- 238000002411 thermogravimetry Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 239000013585 weight reducing agent Substances 0.000 description 2
- OQMIRQSWHKCKNJ-UHFFFAOYSA-N 1,1-difluoroethene;1,1,2,3,3,3-hexafluoroprop-1-ene Chemical group FC(F)=C.FC(F)=C(F)C(F)(F)F OQMIRQSWHKCKNJ-UHFFFAOYSA-N 0.000 description 1
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- 125000004201 2,4-dichlorophenyl group Chemical group [H]C1=C([H])C(*)=C(Cl)C([H])=C1Cl 0.000 description 1
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- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
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- 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
- 229910018071 Li 2 O 2 Inorganic materials 0.000 description 1
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- 229910010707 LiFePO 4 Inorganic materials 0.000 description 1
- 229910015643 LiMn 2 O 4 Inorganic materials 0.000 description 1
- 229910013290 LiNiO 2 Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
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- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- JFBZPFYRPYOZCQ-UHFFFAOYSA-N [Li].[Al] Chemical compound [Li].[Al] JFBZPFYRPYOZCQ-UHFFFAOYSA-N 0.000 description 1
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- YZSKZXUDGLALTQ-UHFFFAOYSA-N [Li][C] Chemical compound [Li][C] YZSKZXUDGLALTQ-UHFFFAOYSA-N 0.000 description 1
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- DNEHKUCSURWDGO-UHFFFAOYSA-N aluminum sodium Chemical compound [Na].[Al] DNEHKUCSURWDGO-UHFFFAOYSA-N 0.000 description 1
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- 150000001450 anions Chemical class 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- BZHNHDOWFCBZNK-UHFFFAOYSA-N antimony lithium Chemical compound [Li].[Sb] BZHNHDOWFCBZNK-UHFFFAOYSA-N 0.000 description 1
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- 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
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- UAZMXAXHGIZMSU-UHFFFAOYSA-N sodium tin Chemical compound [Na].[Sn] UAZMXAXHGIZMSU-UHFFFAOYSA-N 0.000 description 1
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- NSBGJRFJIJFMGW-UHFFFAOYSA-N trisodium;stiborate Chemical compound [Na+].[Na+].[Na+].[O-][Sb]([O-])([O-])=O NSBGJRFJIJFMGW-UHFFFAOYSA-N 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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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
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Description
(式3)
(式4)
例えば、図2に、溶媒和イオン液体、[Li(G3)1][TFSA]の混合比(モル換算)の異なる溶液の熱重量測定結果を示す。測定には、示差熱熱重量同時測定装置(セイコーインスツル社製:TG/DTA 6200)を用い、昇温速度は、10℃/minである。
(2)200〜400℃までの重量減少は、錯形成しているグライムの蒸発に由来する
(3)400℃以上での重量減少は、アルカリ金属塩(LiTFSA)の熱分解に由来する
最初に予備実験として、単体炭素を有する負極とLi金属板からなる正極2とを有する、いわゆるハーフセル構造で、溶媒を含まない電解液(溶媒和イオン液体)の組成(混合比)の異なる二次電池を作製し、充放電特性を評価した。なお、以下、電解液(イオン液体)の組成は、エーテル分子中のエーテル酸素[O]のモル数と、リチウム金属塩のモル数との比 ([O]/[Li])で示す。
上記予備実験で作製した二次電池は、サイクル回数を更に増加すると、サイクル回数の増加につれて放電容量が減少した。これは、60℃と高温のため、活物質である硫黄が何らかの副反応により失活したりしたためと考えた。
また、エーテル酸素の数が少ないG1を用いた電解液を有する二次電池は、エーテル酸素の数が多いG2、G3、G4と比較すると、やはりサイクル特性が劣っていた。
次に、製造されたときに充電状態となっている、リチウム化炭素を有する負極と、単体硫黄を有する正極と、を有する、いわゆるフルセルの二次電池を作製し30℃にて評価した。
ハロゲン原子で置換されていてもよいシクロヘキシル基としては、特に制限はないが、2−クロロシクロヘキシル基、3−クロロシクロヘキシル基、4−クロロシクロヘキシル基、2,4−ジクロロシクロヘキシル基、2−ブロモシクロヘキシル基、3−ブロモシクロヘキシル基、4−ブロモシクロヘキシル基、2,4−ジブロモシクロヘキシル基、2−ヨードシクロヘキシル基、3−ヨードシクロヘキシル基、4−ヨードシクロヘキシル基、2,4−ジヨードシクロヘキシル基等が挙げられる。
4・・・負極(4a:活物質、4b:集電体)
6・・・セパレータ
7・・・電解液
10・・・ガスケット
14・・・スプリング
20・・・コインセルケース
22・・・蓋
50・・・二次電池
Claims (2)
- 充電/放電により炭化リチウムと可逆的に変化する炭素であるグラファイトを負極活物質として有する負極と、
充電/放電により硫化リチウムと可逆的に変化する単体硫黄を正極活物質として有する正極と、
前記負極と前記正極との間に配置されたセパレータと、
リチウム金属塩であるリチウムビス(トリフルオロメタンスルホニル)アミド(LiTFSA)と分子中のエーテル酸素[O]が4個又は5個のグライムとが錯体を形成している溶媒和イオン液体と、前記溶媒和イオン液体と混和すると共にリチウムと化学反応しない、ドナー数が10未満のハイドロフルオロエーテルと、を含み、(グライム分子中のエーテル酸素[O]/リチウム金属塩)のモル比が6未満であり、イオン伝導率(30℃)が、1mS/cm以上であり、粘度(30℃)が、10mPa・s以下で、ポリスルフィド(Li 2 S 8 )の溶解度が、前記ハイドロフルオロエーテルを含まない電解液の1/5以下である電解液と、を具備することを特徴とする二次電池。 - 前記ハイドロフルオロエーテルが、以下のいずれかであることを特徴とする請求項1に記載の二次電池。
HF2CF2CH2C−O−CF2CF2H
F3CH2C−O−CF2CF2H
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EP3214674B1 (en) * | 2014-10-27 | 2019-05-15 | National University Corporation Yokohama National University | Method for producing cathode material for lithium-sulfur battery |
US10541444B2 (en) | 2014-12-26 | 2020-01-21 | Samsung Sdi Co., Ltd. | Rechargeable lithium battery |
JP6100808B2 (ja) * | 2015-01-09 | 2017-03-22 | トヨタ自動車株式会社 | リチウム電池用電解液およびリチウム電池 |
WO2018007665A1 (es) * | 2016-07-04 | 2018-01-11 | Fundación Cidetec | Electrolito basado en il sulfuro/polisulfuro para baterías litio/azufre |
KR102024900B1 (ko) | 2016-11-28 | 2019-09-24 | 주식회사 엘지화학 | 금속 황화물 나노입자를 포함하는 리튬-황 전지용 양극 활물질 및 이의 제조방법 |
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CN112602211B (zh) * | 2018-06-20 | 2023-10-10 | 通用汽车环球科技运作有限责任公司 | 具有盐包水电解质的水基混合锂离子电容器电池 |
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