JP7378032B2 - リチウム二次電池 - Google Patents
リチウム二次電池 Download PDFInfo
- Publication number
- JP7378032B2 JP7378032B2 JP2020534134A JP2020534134A JP7378032B2 JP 7378032 B2 JP7378032 B2 JP 7378032B2 JP 2020534134 A JP2020534134 A JP 2020534134A JP 2020534134 A JP2020534134 A JP 2020534134A JP 7378032 B2 JP7378032 B2 JP 7378032B2
- Authority
- JP
- Japan
- Prior art keywords
- negative electrode
- positive electrode
- lithium
- current collector
- porous membrane
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Links
- 229910052744 lithium Inorganic materials 0.000 title claims description 97
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims description 55
- 239000012528 membrane Substances 0.000 claims description 112
- 239000011255 nonaqueous electrolyte Substances 0.000 claims description 38
- -1 imide anion Chemical class 0.000 claims description 33
- 239000002904 solvent Substances 0.000 claims description 27
- 239000011810 insulating material Substances 0.000 claims description 24
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 23
- 229910001416 lithium ion Inorganic materials 0.000 claims description 23
- 239000002994 raw material Substances 0.000 claims description 20
- 150000001450 anions Chemical class 0.000 claims description 19
- 238000007600 charging Methods 0.000 claims description 18
- 229910003002 lithium salt Inorganic materials 0.000 claims description 17
- 159000000002 lithium salts Chemical class 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 17
- 150000003839 salts Chemical class 0.000 claims description 17
- 239000007774 positive electrode material Substances 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 15
- 229910052723 transition metal Inorganic materials 0.000 claims description 14
- 150000003624 transition metals Chemical class 0.000 claims description 14
- 239000002131 composite material Substances 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 7
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 claims description 6
- 229910052796 boron Inorganic materials 0.000 claims description 6
- 229920000178 Acrylic resin Polymers 0.000 claims description 5
- 239000004925 Acrylic resin Substances 0.000 claims description 5
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 5
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 5
- 229920001721 polyimide Polymers 0.000 claims description 5
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 claims description 4
- 239000009719 polyimide resin Substances 0.000 claims description 4
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- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 claims description 3
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- 239000011242 organic-inorganic particle Substances 0.000 claims 4
- 239000000919 ceramic Substances 0.000 claims 2
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- 239000010408 film Substances 0.000 description 27
- 235000002639 sodium chloride Nutrition 0.000 description 18
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 13
- 210000001787 dendrite Anatomy 0.000 description 13
- 150000001768 cations Chemical class 0.000 description 10
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 8
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- 238000004519 manufacturing process Methods 0.000 description 7
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- 238000001878 scanning electron micrograph Methods 0.000 description 6
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- 238000000151 deposition Methods 0.000 description 5
- 238000007599 discharging Methods 0.000 description 5
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
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- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
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- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 4
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- 239000000463 material Substances 0.000 description 4
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- 238000001556 precipitation Methods 0.000 description 4
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- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 3
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- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 3
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- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
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- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- 229910015760 LiNi0.8Co0.18Al0.02O2 Inorganic materials 0.000 description 2
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
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- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 229920002125 Sokalan® Polymers 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
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- 238000010586 diagram Methods 0.000 description 2
- MHDVGSVTJDSBDK-UHFFFAOYSA-N dibenzyl ether Chemical compound C=1C=CC=CC=1COCC1=CC=CC=C1 MHDVGSVTJDSBDK-UHFFFAOYSA-N 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- GAEKPEKOJKCEMS-UHFFFAOYSA-N gamma-valerolactone Chemical compound CC1CCC(=O)O1 GAEKPEKOJKCEMS-UHFFFAOYSA-N 0.000 description 2
- 239000000499 gel Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 150000003949 imides Chemical class 0.000 description 2
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 2
- 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 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000001465 metallisation Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
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- 239000004584 polyacrylic acid Substances 0.000 description 2
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- MIZLGWKEZAPEFJ-UHFFFAOYSA-N 1,1,2-trifluoroethene Chemical compound FC=C(F)F MIZLGWKEZAPEFJ-UHFFFAOYSA-N 0.000 description 1
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 description 1
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 1
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 1
- UNDXPKDBFOOQFC-UHFFFAOYSA-N 4-[2-nitro-4-(trifluoromethyl)phenyl]morpholine Chemical compound [O-][N+](=O)C1=CC(C(F)(F)F)=CC=C1N1CCOCC1 UNDXPKDBFOOQFC-UHFFFAOYSA-N 0.000 description 1
- SBUOHGKIOVRDKY-UHFFFAOYSA-N 4-methyl-1,3-dioxolane Chemical compound CC1COCO1 SBUOHGKIOVRDKY-UHFFFAOYSA-N 0.000 description 1
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- 229920000049 Carbon (fiber) Polymers 0.000 description 1
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- SYRDSFGUUQPYOB-UHFFFAOYSA-N [Li+].[Li+].[Li+].[O-]B([O-])[O-].FC(=O)C(F)=O Chemical compound [Li+].[Li+].[Li+].[O-]B([O-])[O-].FC(=O)C(F)=O SYRDSFGUUQPYOB-UHFFFAOYSA-N 0.000 description 1
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- QHIWVLPBUQWDMQ-UHFFFAOYSA-N butyl prop-2-enoate;methyl 2-methylprop-2-enoate;prop-2-enoic acid Chemical compound OC(=O)C=C.COC(=O)C(C)=C.CCCCOC(=O)C=C QHIWVLPBUQWDMQ-UHFFFAOYSA-N 0.000 description 1
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- 239000010936 titanium Substances 0.000 description 1
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- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
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- 229910052727 yttrium Inorganic materials 0.000 description 1
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- 239000011701 zinc Substances 0.000 description 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc oxide Inorganic materials [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
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Description
負極は、充電時にリチウム金属が析出する電極である。負極集電体の表面に析出したリチウム金属は、放電により非水電解質中にリチウムイオンとして溶解する。析出するリチウム金属は非水電解質中のリチウムイオンに由来する。非水電解質に含まれるリチウムイオンは、非水電解質に添加したリチウム塩に由来するものであってもよく、充電により正極活物質から供給されるものであってもよく、これらの双方であってもよい。また、多孔質膜の製造に用いられる原料(後述参照)由来のリチウム塩であってもよい。
多孔質膜は、負極集電体の少なくとも一方の主面に、多孔質膜の原料液を塗布することにより形成される。負極は、例えば、負極集電体を準備する第1工程と、負極集電体の少なくとも一方の主面に、第2多孔質膜の原料液(第2原料液)を塗布した後、乾燥し、第2多孔質膜を形成する第2工程と、負極集電体の第2多孔質膜が形成された主面に第1多孔質膜の原料液(第1原料液)を塗布した後、乾燥し、第1多孔質膜を形成する第3工程と、を備える方法により製造される。
正極は、正極活物質を含む正極合剤層と、正極集電体と、を備える。正極合剤層は、正極活物質、結着剤および導電剤などを含む正極合剤を分散媒に分散させた正極スラリーを、正極集電体の表面に塗布し、乾燥させることにより形成できる。乾燥後の塗膜を、必要により圧延してもよい。正極合剤層は、正極集電体の一方の表面に形成してもよく、両方の表面に形成してもよい。
非水電解質としては、リチウムイオン伝導性を有するものが使用される。このような非水電解質は、非水溶媒と、非水溶媒に溶解したリチウムイオンおよびアニオンとを含んでいる。非水電解質は、液状であってもよいし、ゲル状であってもよい。
正極と負極との間には、セパレータを介在させる。セパレータは、イオン透過度が高く、適度な機械的強度および絶縁性を備えている。セパレータとしては、微多孔薄膜、織布、不織布などを用いることができる。セパレータの材質としては、ポリプロピレン、ポリエチレンなどのポリオレフィンが好ましい。
図3は、本発明の一実施形態に係る円筒型のリチウム二次電池の一例の縦断面図である。
(1)正極の作製
リチウムニッケル複合酸化物(LiNi0.8Co0.18Al0.02O2)と、アセチレンブラックと、PVdFとを、95:2.5:2.5の質量比で混合し、NMPを添加した後、混合機(プライミクス社製、T.K.ハイビスミックス)を用いて攪拌し、正極スラリーを調製した。次に、Al箔の表面に正極スラリーを塗布し、塗膜を乾燥させた後、圧延して、Al箔の両面に、密度3.6g/cm3の正極合剤層が形成された正極を作製した。
電解銅箔(厚み10μm)を所定の電極サイズに切断した。PVdF(濃度8質量%)、LiTFSI(濃度1質量%)、NMPを含む原料液を準備した。
FECとEMCとDMCとを、FEC:EMC:DMC=20:5:75の容積比で混合した。得られた混合溶媒に、リチウムジフルオロオキサレートボレートを0.3mol/L、LiPF6を1.0mol/Lとなるようにそれぞれ溶解させて、非水電解質を調製した。
上記で得られた正極に、Al製のタブを取り付けた。上記で得られた負極に、Ni製のタブを取り付けた。不活性ガス雰囲気中で、正極と負極とをポリエチレン薄膜(セパレータ)を介して渦巻状に捲回し、捲回型の電極体を作製した。得られた電極体を、Al層を備えるラミネートシートで形成される袋状の外装体に収容し、上記非水電解質を注入した後、外装体を封止してリチウム二次電池T1を作製した。
負極の作製(2)において、第1多孔質膜の第1厚さを1μmにしたこと以外は、実施例1と同様にしてリチウム二次電池T2を作製した。
負極の作製(2)において、第2多孔質膜と第1多孔質膜との間に、2つの層からなる第3多孔質膜(第3厚さ:1μm=0.5μm×2)を形成したこと以外は、実施例1と同様にしてリチウム二次電池T3を作製した。
負極の作製(2)において、同じ原料液を用いて、厚さ2μmの多孔質膜を1層形成したこと以外は、実施例1と同様にしてリチウム二次電池R1を作製した。
負極の作製(2)において、LiTFSIを含まない原料液を用いたこと以外は、実施例1と同様にしてリチウム二次電池R2を作製した。
得られた電池T1~T3、R1、R2について、充放電試験を行った。
(充電)20mAの電流で電池電圧が4.1Vになるまで定電流充電を行い、その後、4.1Vの電圧で電流値が2mAになるまで定電圧充電を行った。
(放電)20mAの電流で電池電圧が3.0Vになるまで定電流放電を行った。
50サイクルの充放電を行った後、電池を解体して負極を取り出した。この負極を厚み方向に切断して、断面を走査型電子顕微鏡(SEM)で観察した。評価結果を表1に示す。図4Aに、電池T1から取り出された負極の断面のSEM画像(倍率2500倍)を示す。図4Bに、図4AのSEM画像の一部を拡大して示す。なお、図4Bでは、便宜的に、第1多孔質膜22Aと第2多孔質膜22Bとの界面を破線で示している。図4Aおよび図4Bによれば、リチウム金属(Li)は、負極集電体21と第2多孔質膜22Bとの間に析出している。図5に、電池R1から取り出された負極の断面のSEM画像(倍率2500倍)を示す。図5によれば、リチウム金属(Li)は、多孔質膜22の負極集電体21に対向しない主面(図示されないセパレータ側の主面)に析出している。
50サイクル目の放電容量を1サイクル目の放電容量で割った値を容量維持率(%)とした。評価結果を表1に示す。
13 正極リード
15 正極端子
20 負極
21 負極集電体
22A 第1多孔質膜
22B 第2多孔質膜
23 負極リード
30 セパレータ
40 捲回式電極群
60 下部絶縁リング
70 電池ケース
80 上部絶縁リング
90 封口板
100 リチウム二次電池
22 多孔質膜
Claims (10)
- 正極と、負極と、リチウムイオン伝導性の非水電解質と、前記正極と前記負極との間に配置されるセパレータと、を備え、
前記正極は、正極活物質を含む正極合剤層と、正極集電体と、を備え、
前記正極活物質は、リチウムと遷移金属とを含む複合酸化物を含み、
前記正極および前記負極が有する単位面積当たりのリチウムの合計量MLiと、前記正極が有する単位面積当たりの遷移金属量MTMとのモル比:MLi/MTMは、1.1以下であり、
前記負極は、負極集電体と、前記負極集電体上に積層された複数の絶縁性の多孔質膜(ただし、セラミックス、有機粒子、無機粒子および有無機粒子の1種以上を合計で70質量%以上含む場合を除く)と、を備え、
前記複数の絶縁性の多孔質膜が、互いに接触し、
前記複数の絶縁性の多孔質膜は、第1多孔質膜と、前記第1多孔質膜と前記負極集電体との間に配置された第2多孔質膜と、を備え、
前記第1多孔質膜の貫通孔を第1貫通孔、前記第2多孔質膜の貫通孔を第2貫通孔としたとき、前記第2貫通孔の平均径は、前記第1貫通孔の平均径より小さく、
前記第1多孔質膜の厚さは、前記第2多孔質膜の厚さ以上であり、
前記第1多孔質膜の厚さは、前記第2多孔質膜の厚さに対して1.1倍以上であり、
充電時、前記負極集電体の表面と前記第1多孔質膜との間にリチウム金属が析出する、リチウム二次電池。 - 前記第1多孔質膜の厚さは0.1μm以上、2μm以下であり、
前記第2多孔質膜の厚さは0.1μm以上、1μm以下である、請求項1に記載のリチウム二次電池。 - 前記複数の絶縁性の多孔質膜は、いずれも前記正極合剤層に対向する対向領域を有し、
前記複数の絶縁性の多孔質膜の少なくとも一つは、前記正極合剤層に対向しない非対向領域を有し、
前記非対向領域の少なくとも一部は、充電状態において、前記負極集電体に接触している、請求項1または2に記載のリチウム二次電池。 - 前記複数の絶縁性の多孔質膜の少なくとも一つは、フッ化ビニリデン由来のユニットを有する高分子を含む、請求項1~3のいずれか一項に記載のリチウム二次電池。
- 前記複数の絶縁性の多孔質膜の少なくとも一つは、リチウム塩および常温溶融塩の少なくとも一種を含む、請求項1~4のいずれか一項に記載のリチウム二次電池。
- 前記非水電解質は、フルオロエチレンカーボネートおよびビニレンカーボネートの少なくとも一方を含む、請求項1~5のいずれか一項に記載のリチウム二次電池。
- 前記非水電解質は、リチウムイオンとアニオンとを含み、
前記アニオンは、イミド類のアニオンおよびホウ素を含むオキサレート類のアニオンの少なくとも一種を含む、請求項1~6のいずれか一項に記載のリチウム二次電池。 - 前記イミド類のアニオンは、ビス(フルオロスルホニル)イミドアニオンおよびビストリフルオロメチルスルホニルイミドアニオンの少なくとも一方である、請求項7に記載のリチウム二次電池。
- 正極と、負極と、リチウムイオン伝導性の非水電解質と、前記正極と前記負極との間に配置されるセパレータと、を備え、
前記正極は、正極活物質を含む正極合剤層と、正極集電体と、を備え、
前記正極活物質は、リチウムと遷移金属とを含む複合酸化物を含み、
前記正極および前記負極が有する単位面積当たりのリチウムの合計量MLiと、前記正極が有する単位面積当たりの遷移金属量MTMとのモル比:MLi/MTMは、1.1以下であり、
前記負極は、負極集電体と、前記負極集電体上に積層された複数の絶縁性の多孔質膜(ただし、セラミックス、有機粒子、無機粒子および有無機粒子の1種以上を合計で70質量%以上含む場合を除く)と、を備え、
前記複数の多孔質膜の境界には界面が存在し、
前記複数の絶縁性の多孔質膜は、絶縁性材料で構成され、
前記絶縁性材料は、フッ素樹脂、ポリアクリロニトリル、ポリイミド樹脂、アクリル樹脂、ポリオレフィン樹脂、ウレタン樹脂、ポリカーボネート樹脂およびエポキシ樹脂から選択され、
前記複数の多孔質膜が、互いに接触し、
充電時、前記負極集電体の表面と前記第1多孔質膜との間にリチウム金属が析出する、リチウム二次電池。 - 正極と、負極と、リチウムイオン伝導性の非水電解質と、前記正極と前記負極との間に配置されるセパレータと、を備え、
前記正極は、正極活物質を含む正極合剤層と、正極集電体と、を備え、
前記正極活物質は、リチウムと遷移金属とを含む複合酸化物を含み、
前記正極および前記負極が有する単位面積当たりのリチウムの合計量MLiと、前記正極が有する単位面積当たりの遷移金属量MTMとのモル比:MLi/MTMは、1.1以下であり、
前記負極は、負極集電体と、前記負極集電体上に積層された複数の絶縁性の多孔質膜と、を備え、
前記複数の絶縁性の多孔質膜は、前記負極集電体の少なくとも一方の主面に、前記多孔質膜の原料液を塗布した後、乾燥する工程を、少なくとも2回繰り返すことにより形成され、
前記原料液は、絶縁性材料と、前記絶縁性材料を溶解する溶媒と、を含み、
前記原料液中の前記絶縁性材料の濃度は、3質量%以上35質量%以下であり、
前記絶縁性材料は、フッ素樹脂、ポリアクリロニトリル、ポリイミド樹脂、アクリル樹脂、ポリオレフィン樹脂、ウレタン樹脂、ポリカーボネート樹脂およびエポキシ樹脂から選択され、
充電時、前記負極集電体の表面と前記第1多孔質膜との間にリチウム金属が析出する、リチウム二次電池。
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