JP2021018962A - リチウムイオン二次電池の製造方法及びリチウムイオン二次電池 - Google Patents
リチウムイオン二次電池の製造方法及びリチウムイオン二次電池 Download PDFInfo
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- JP2021018962A JP2021018962A JP2019135655A JP2019135655A JP2021018962A JP 2021018962 A JP2021018962 A JP 2021018962A JP 2019135655 A JP2019135655 A JP 2019135655A JP 2019135655 A JP2019135655 A JP 2019135655A JP 2021018962 A JP2021018962 A JP 2021018962A
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- Prior art keywords
- secondary battery
- ion secondary
- lithium ion
- lithium
- negative electrode
- 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.)
- Granted
Links
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 44
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 26
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 29
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000002608 ionic liquid Substances 0.000 claims abstract description 24
- -1 bis (fluorosulfonyl) imide anion Chemical class 0.000 claims abstract description 17
- 239000003792 electrolyte Substances 0.000 claims abstract description 16
- 239000003365 glass fiber Substances 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims description 30
- 150000001450 anions Chemical class 0.000 claims description 18
- 125000000129 anionic group Chemical group 0.000 abstract 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 13
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 12
- 239000007774 positive electrode material Substances 0.000 description 10
- 239000011230 binding agent Substances 0.000 description 9
- 229910052799 carbon Inorganic materials 0.000 description 9
- 239000008151 electrolyte solution Substances 0.000 description 9
- 239000007773 negative electrode material Substances 0.000 description 9
- 239000002033 PVDF binder Substances 0.000 description 8
- 229910052782 aluminium Inorganic materials 0.000 description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 8
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 8
- 229910003002 lithium salt Inorganic materials 0.000 description 7
- 159000000002 lithium salts Chemical class 0.000 description 7
- 238000002347 injection Methods 0.000 description 6
- 239000007924 injection Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
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- 150000001768 cations Chemical class 0.000 description 5
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- 239000007772 electrode material Substances 0.000 description 5
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- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000004020 conductor Substances 0.000 description 4
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- 239000010439 graphite Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
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- 229910044991 metal oxide Inorganic materials 0.000 description 4
- 150000004706 metal oxides Chemical class 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- 150000003624 transition metals Chemical class 0.000 description 4
- 229910010941 LiFSI Inorganic materials 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 description 3
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- BLTXWCKMNMYXEA-UHFFFAOYSA-N 1,1,2-trifluoro-2-(trifluoromethoxy)ethene Chemical compound FC(F)=C(F)OC(F)(F)F BLTXWCKMNMYXEA-UHFFFAOYSA-N 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 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
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- 125000004122 cyclic group Chemical group 0.000 description 2
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- 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
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- IQQRAVYLUAZUGX-UHFFFAOYSA-N 1-butyl-3-methylimidazolium Chemical compound CCCCN1C=C[N+](C)=C1 IQQRAVYLUAZUGX-UHFFFAOYSA-N 0.000 description 1
- NJMWOUFKYKNWDW-UHFFFAOYSA-N 1-ethyl-3-methylimidazolium Chemical compound CCN1C=C[N+](C)=C1 NJMWOUFKYKNWDW-UHFFFAOYSA-N 0.000 description 1
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0568—Liquid materials characterised by the solutes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
-
- 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
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Abstract
Description
電解質として、ビス(フルオロスルホニル)イミドアニオンをアニオン成分として含むイオン液体を用い、
正極と負極との間に設けたセパレータとして、空隙率が70%以上であるガラス繊維を用いる、リチウムイオン二次電池の製造方法であって、
前記正極と、前記負極と、前記セパレータと、前記電解質とを用いたリチウム二次電池中間体を準備する工程と、
35℃以上75℃以下で8時間以上30時間以下の高温処理を前記リチウム二次電池中間体に行う工程と、を含む。
A1.リチウムイオン二次電池の製造方法
本発明の一実施形態であるリチウムイオン二次電池の製造方法は、(i)正極と、負極と、セパレータと、電解質とを用いたリチウム二次電池中間体を準備する工程(以下、「準備工程」とも呼ぶ)と、(ii)35℃以上75℃以下で8時間以上30時間以下の高温処理をリチウム二次電池中間体に行う工程と、を含む。
本実施形態に係るリチウムイオン電池は、正極と、負極と、セパレータと、非水電解液と、を備える。
空隙率(%)=100−(セパレータの見掛け密度/材料固形分の真密度)×100
以下、実施例により本発明をさらに具体的に説明するが、本発明は以下の実施例に限定されない。
[正極の作製]
正極活物質としてLiNi1/3Mn1/3Co1/3O2を90g、導電剤としてSuperP(登録商標)(Timcal社製)を4gとTIMREX(登録商標)KS6(Timcal社製)を2g、バインダーとしてポリフッ化ビニリデン(PVDF)(クレハ社製)を4g、分散媒としてN−メチル−2−ピロリドンを47g、を遊星式ミキサーで混合することにより、固形分68質量%の正極塗料を得た。塗工機を用いて、集電体としてのアルミ箔(厚み15μm)上にこの正極塗料を塗布した後、130℃で減圧乾燥後、ロールプレス処理を行うことにより正極を得た。
負極活物質として黒鉛を95.5g、導電剤としてSuperP(登録商標)(Timcal社製)を0.5g、増粘剤としてCMC(第一工業製薬社製)を2g、バインダーとしてSBR(JSR社製)を2g、分散媒として純水を100g、を遊星式ミキサーで混合することにより、固形分49質量%の負極塗料を得た。塗工機を用いて、集電体としての電解銅箔(厚み10μm)上にこの負極塗料を塗布した後、130℃で減圧乾燥後、ロールプレス処理を行うことにより負極を得た。
上述の正極と上述の負極との間に、セパレータとして厚み30[μm]のガラス繊維を挟んだ構造の積層体を作製した後、正極に正極端子を超音波溶接するとともに、負極に負極端子を超音波溶接した。その後、この積層体をアルミラミネート包材に入れ、注液用の開口部を残して封止することにより、注液前電池を得た。本実施例では、正極面積を18cm2とし、負極面積を19.35cm2とした。次に、N−メチル−N−プロピルピロリジニウムとFSIとの混合溶媒に、1.2mol/kgのLiFSIを溶解した溶液を電解液として、この注液前電池に注入した後、開口部を封止することにより、リチウム二次電池中間体を得た。
得られたリチウム二次電池中間体について、冶具などによる拘束は実施せず、恒温槽内に静置し、50℃12時間の高温処理を行った。以上の工程を経ることにより、リチウムイオン二次電池を得た。
初回充放電効率を算出するための試験として、作製したリチウムイオン二次電池を、0.2C電流値にて12時間のCCCV(Constant Current, Constant Voltage:定電流定電圧)充電した後、0.2C電流値にてCC(Constant Current:定電流)放電を実施した。充放電の電圧範囲は2.7V−4.2Vに設定した。初回充放電効率は、初回充電容量に対する初回放電容量の比率(初回放電容量/初回充電容量)を示す。なお、0.2C電流値とは、セル容量を1時間で放電できる電流値1Cの0.2倍の電流値を示す。
Claims (5)
- 電解質として、ビス(フルオロスルホニル)イミドアニオンをアニオン成分として含むイオン液体を用い、
正極と負極との間に設けたセパレータとして、空隙率が70%以上であるガラス繊維を用いる、リチウムイオン二次電池の製造方法であって、
前記正極と、前記負極と、前記セパレータと、前記電解質とを用いたリチウム二次電池中間体を準備する工程と、
35℃以上75℃以下で8時間以上30時間以下の高温処理を前記リチウム二次電池中間体に行う工程と、を含む、リチウムイオン二次電池の製造方法。 - 請求項1に記載のリチウムイオン二次電池の製造方法であって、
前記高温処理は、45℃以上75℃以下で行う、リチウムイオン二次電池の製造方法。 - 請求項1又は請求項2に記載のリチウムイオン二次電池の製造方法であって、
前記高温処理は、10時間以上24時間以下行う、リチウムイオン二次電池の製造方法。 - 請求項1から請求項3までのいずれか1項に記載のリチウムイオン二次電池の製造方法によって製造されたリチウムイオン二次電池。
- リチウムイオン二次電池であって、
正極と、
負極と、
正極と負極との間に設けられ、空隙率が70%以上であるガラス繊維を用いたセパレータと、
ビス(フルオロスルホニル)イミドアニオンをアニオン成分として含むイオン液体を用いる電解質と、を備え、
初回充放電効率が80%以上である、リチウムイオン二次電池。
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JP2010287380A (ja) * | 2009-06-10 | 2010-12-24 | Dai Ichi Kogyo Seiyaku Co Ltd | イオン液体を用いたリチウム二次電池 |
JP2016189239A (ja) * | 2015-03-30 | 2016-11-04 | 日立化成株式会社 | リチウムイオン二次電池 |
JP2018152519A (ja) * | 2017-03-14 | 2018-09-27 | 株式会社リコー | 非水系蓄電素子 |
JP2019106367A (ja) * | 2017-12-11 | 2019-06-27 | トヨタ自動車株式会社 | 非水電解液二次電池および非水電解液二次電池の製造方法 |
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JP2010287380A (ja) * | 2009-06-10 | 2010-12-24 | Dai Ichi Kogyo Seiyaku Co Ltd | イオン液体を用いたリチウム二次電池 |
JP2016189239A (ja) * | 2015-03-30 | 2016-11-04 | 日立化成株式会社 | リチウムイオン二次電池 |
JP2018152519A (ja) * | 2017-03-14 | 2018-09-27 | 株式会社リコー | 非水系蓄電素子 |
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