TW201503461A - 循環鋰硫電池之方法 - Google Patents
循環鋰硫電池之方法 Download PDFInfo
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- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 238000000034 method Methods 0.000 title claims abstract description 26
- 230000001351 cycling effect Effects 0.000 title abstract 2
- 238000007599 discharging Methods 0.000 claims abstract description 11
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 39
- 229910052717 sulfur Inorganic materials 0.000 claims description 30
- 239000011593 sulfur Substances 0.000 claims description 30
- 239000000463 material Substances 0.000 claims description 23
- 239000003792 electrolyte Substances 0.000 claims description 15
- 238000012544 monitoring process Methods 0.000 claims description 3
- 230000008878 coupling Effects 0.000 claims description 2
- 238000010168 coupling process Methods 0.000 claims description 2
- 238000005859 coupling reaction Methods 0.000 claims description 2
- 239000004020 conductor Substances 0.000 description 14
- 229910052744 lithium Inorganic materials 0.000 description 13
- -1 flakes Chemical class 0.000 description 12
- 239000000203 mixture Substances 0.000 description 12
- 239000005077 polysulfide Substances 0.000 description 7
- 229920001021 polysulfide Polymers 0.000 description 7
- 150000008117 polysulfides Polymers 0.000 description 7
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
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- 239000011888 foil Substances 0.000 description 5
- 229910003002 lithium salt Inorganic materials 0.000 description 5
- 159000000002 lithium salts Chemical class 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
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- 238000012733 comparative method Methods 0.000 description 3
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- MCVFFRWZNYZUIJ-UHFFFAOYSA-M lithium;trifluoromethanesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C(F)(F)F MCVFFRWZNYZUIJ-UHFFFAOYSA-M 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
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- DIIIISSCIXVANO-UHFFFAOYSA-N 1,2-Dimethylhydrazine Chemical compound CNNC DIIIISSCIXVANO-UHFFFAOYSA-N 0.000 description 2
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 2
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- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
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- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 2
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
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- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
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- 229910052684 Cerium Inorganic materials 0.000 description 1
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- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
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- 229920002943 EPDM rubber Polymers 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 229910018091 Li 2 S Inorganic materials 0.000 description 1
- 229910015015 LiAsF 6 Inorganic materials 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
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- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
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- 239000010406 cathode material Substances 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- HQFQTTNMBUPQAY-UHFFFAOYSA-N cyclobutylhydrazine Chemical compound NNC1CCC1 HQFQTTNMBUPQAY-UHFFFAOYSA-N 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000011263 electroactive material Substances 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 1
- 150000002429 hydrazines Chemical class 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 150000002641 lithium Chemical class 0.000 description 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- KKQAVHGECIBFRQ-UHFFFAOYSA-N methyl propyl carbonate Chemical compound CCCOC(=O)OC KKQAVHGECIBFRQ-UHFFFAOYSA-N 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- VQSLYBNAHOGNCE-UHFFFAOYSA-N pentan-3-yl propanoate Chemical compound CCC(CC)OC(=O)CC VQSLYBNAHOGNCE-UHFFFAOYSA-N 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
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- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- 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
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/44—Methods for charging or discharging
-
- 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
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/44—Methods for charging or discharging
- H01M10/448—End of discharge regulating measures
-
- 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
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/46—Accumulators structurally combined with charging apparatus
-
- H—ELECTRICITY
- H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
- H02J—CIRCUIT ARRANGEMENTS OR SYSTEMS FOR SUPPLYING OR DISTRIBUTING ELECTRIC POWER; SYSTEMS FOR STORING ELECTRIC ENERGY
- H02J7/00—Circuit arrangements for charging or depolarising batteries or for supplying loads from batteries
- H02J7/0029—Circuit arrangements for charging or depolarising batteries or for supplying loads from batteries with safety or protection devices or circuits
-
- H—ELECTRICITY
- H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
- H02J—CIRCUIT ARRANGEMENTS OR SYSTEMS FOR SUPPLYING OR DISTRIBUTING ELECTRIC POWER; SYSTEMS FOR STORING ELECTRIC ENERGY
- H02J7/00—Circuit arrangements for charging or depolarising batteries or for supplying loads from batteries
- H02J7/007—Regulation of charging or discharging current or voltage
- H02J7/00712—Regulation of charging or discharging current or voltage the cycle being controlled or terminated in response to electric parameters
- H02J7/007182—Regulation of charging or discharging current or voltage the cycle being controlled or terminated in response to electric parameters in response to battery voltage
- H02J7/007184—Regulation of charging or discharging current or voltage the cycle being controlled or terminated in response to electric parameters in response to battery voltage in response to battery voltage gradient
-
- H02J7/0086—
-
- 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
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/425—Structural combination with electronic components, e.g. electronic circuits integrated to the outside of the casing
- H01M2010/4271—Battery management systems including electronic circuits, e.g. control of current or voltage to keep battery in healthy state, cell balancing
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Power Engineering (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Charge And Discharge Circuits For Batteries Or The Like (AREA)
Abstract
一種循環鋰硫電池之方法,該方法包含放電鋰硫電池,當電池的電壓達到1.5到2.1V範圍內的閾值放電電壓時終止放電,充電鋰硫電池,以及當電池電壓達到2.3到2.4V範圍內的閾值充電電壓時終止充電,其中該鋰硫電池在閾值充電電壓時未完全充電,且其中該鋰硫電池在閾值放電電壓時未完全放電。
Description
本發明係關於一種循環鋰硫電池組之方法。本發明亦關於一種用於循環鋰硫電池組的電池組管理系統。
典型的鋰硫電池包含由鋰金屬或鋰金屬合金形成的一陽極(負極),及由元素硫或其他電活性硫材料形成之一陰極(正極)。硫或其他電活性含硫材料可與例如碳的導電材料混合,以改善導電材料的導電性。一般而言,研磨碳及硫並接著與溶劑及黏合劑混合成為一漿料。將此漿料施加至一集電器並接著乾燥以移除溶劑。壓延所獲得之結構以形成複合結構,將此複合結構切割成所欲形狀以形成陰極。將分隔件置於陰極上且將鋰陽極置於分隔件上。接著將電解質注入此組裝電池中以濕潤陰極和分隔件。
鋰硫電池為二次電池。當鋰硫電池放電時,在陰極的硫以二階段方式還原。在第一階段中,硫(例如元素硫)還原成多硫化物種類,Sn 2-(n2)。這些種類通常可溶於電解質內。在放電的第二階段中,多硫化物種類還原成硫化鋰,Li2S,其一般沉積在陽極表面。
當電池充電時,隨著硫化鋰氧化成多硫化鋰並接著氧化成鋰和硫,二階段機制逆向發生。此二階段機制在鋰硫電池之放電及充電分布曲線皆可看到。因此,當鋰硫電池充電時,其電壓一般會通過當電池在第一階段及第二階段之間轉換的反曲點。
鋰硫電池為二次電池且可經由施與外部電流而(再)充電。一般而言,電池係充電至固定之截止電壓,例如2.45至2.8V。然而,隨著一段延長時間的重覆循環,電池電容可能消退。當然,經過一定數目的循環後,因為電池的內電阻增加而可能不再有可能使電池充電至固定之截止電壓。藉由重覆對電池充電至所選定之截止電壓,此電池最後可能會重覆地過量充電。如此對電池的長壽能有不利影響,因為非所欲之化學反應可能導致例如電池電極及/或電解質之劣化。
基於前述,理想的是避免過量-充電鋰硫電池。WO 2007/111988描述一種用於決定鋰硫電池何時完全充電的方法。具體而言,此參考文獻描述將例如硝酸鋰的N-O添加物添加至電池的電解質。根據此參考文獻的第16頁第29到31行,此添加物可有效地提供在瀕臨完全充電時電壓急劇增加的充電曲線圖。因此,若在充電期間監測電池電壓,一旦觀察到電壓快速增加,即可終止充電。
WO 2007/111988的方法倚賴當電池達到完全電容時,電池電壓的急劇增加。然而,並非所有的鋰硫電池均表現出如此之充電分布曲線。
根據本發明,提供一種循環鋰硫電池之方法,該方法包含:(i)放電鋰硫電池,(ii)當電池的電壓達到1.5到2.1V範圍內的閾值放電電壓時終止放電,(iii)充電鋰硫電池,以及(iv)當電池電壓達到2.3到2.4V範圍內的閾值充電電壓時終止充電,其中該鋰硫電池在閾值充電電壓時未完全充電,以及其中該鋰硫電池在閾值放電電壓時未完全放電。
不希望受任何理論束縛,已發現到藉由使鋰硫電池充電不足及可選擇地放電不足能夠有利地降低電容消退的速率。當鋰硫電池完全充電時,例如元素硫之電活性硫材料通常是以其完全氧化型式(例如S8)存在。在此型式中,電活性硫材料一般是非導電性。因此,當此材料(例如元素硫)沉積在陰極上時,陰極的電阻可能增加。如此可能導致溫度的增加,其隨著延長的循環,可能導致電池組件劣化更快。如此接著可能降低電池的電容,且增加電容消退的速率。相似地,當此電池在其完全放電狀態時,硫化鋰沉積在負極上。如此亦能夠具有增加電池電阻的效果。藉由使此電池充電-不足及可選擇地放電不足,所產生之非導電性種類的數量可能降低,藉此降低電池電阻及電容消退的
趨勢。
在一實施例中,電池充電至顯著比例的陰極硫材料(例如元素硫)仍溶解於電解質(例如多硫化物)之階段。電池亦可放電至顯著比例的陰極硫材料(例如元素硫)仍溶解於電解質(例如多硫化物)的點。較佳地,當至少80%的陰極硫材料溶解於電解質(例如多硫化物)時,發生終止充電及可選擇地放電的點。陰極硫材料溶解於溶液內之百分比可藉由已知方法決定,例如,由電池內殘餘固體硫的量來決定,該量為引入做為陰極材料之硫材料的初始量的百分比。
閾值放電電壓為1.5到2.1V,例如1.5到1.8V或由1.8V到2.1V。適當的閾值放電電壓範圍為1.6到2.0V,例如1.7到1.9V。較佳地,閾值放電電壓為1.7到1.8V,較佳為約1.75V。
較佳地,閾值充電電壓為約2.30到2.36V,更佳為2.30到2.35V,又更佳為2.31到2.34V,例如2.33V。
在一實施例中,例如在電池的整個有效壽命期間,重覆步驟(i)至(iv)至少2個放電-充電循環,較佳地至少20個放電-充電循環,更佳地至少100個循環。
在一實施例中,此方法進一步包含在充電及/或放電期間,監測電池電壓的步驟。
本發明亦提供一種用於實現上述方法的電池組管理系統。
根據本發明之另一方面,提供一種用於控制鋰硫
電池之放電及充電之電池組管理系統,該系統包含:用於在高於該電池完全充電狀態下的電池電壓的閾值放電電壓下,終止該鋰硫電池放電的裝置,用於充電該鋰硫電池之裝置,以及用於在低於該電池完全充電狀態下的電池電壓的閾值充電電壓下,終止該鋰硫電池充電的裝置。
較佳地,此系統方包含在充電及放電期間用於監測電池電壓的裝置。
在一實施例中,當電池電壓在1.5到1.8V,較佳地在1.7到1.8V,例如約1.75V時,用於終止電池放電的裝置終止放電。
擇一地或額外地,用於終止電池充電的裝置,在當電池電壓在2.3到2.4V時終止充電。較佳地,在約2.30到2.36V時終止充電電壓,更佳地為2.30到2.35V時,又更佳地為2.31到2.34V時,例如2.33V。
此系統可包括用於耦合此系統至鋰硫電池或電池組的裝置。較佳地,此系統包括鋰硫電池或電池組。
在一較佳的實施例中,鋰硫電池藉由在固定電流之下提供電能來充電。可提供電流以致能在30分鐘至12小時的時間範圍內充電電池,較佳為8到10小時。此電流可在0.1到3mA/cm2的電流密度範圍下提供,較佳地為0.1到0.3mA/cm2。作為在固定電流下充電之另一選擇,也可能充電鋰硫電池至一固定電壓直到達到相關電容。
此電化學電池可為任何適合之鋰硫電池。此電池
通常地包括一陽極、一陰極,一電解質以及較佳地,可有利地置於陽極與陰極之間的多孔性分隔件。陽極可由鋰金屬或鋰金屬合金形成。較佳地,此陽極為金屬箔電極,例如鋰箔電極。此鋰箔可由鋰金屬或鋰金屬合金形成。
此電化學電池的陰極包括電活性硫材料及導電材料之混合物。此混合物形成電活性層,可被放置以與集電器接觸。
電活性硫材料及導電材料的混合物可以存在於溶劑(例如水或有機溶劑)中之漿料的形式施用至集電器。溶劑可接著被移除且所獲得之結構被壓延以形成複合結構,該複合結構被切割成所欲之形狀以形成陰極。一分隔件可被放置於該陰極上且鋰陽極被置於該分隔件上。電解質可接著被注入此組裝電池以濕潤該陰極和分隔件。
電活性硫材料可包含元素硫、以硫為主的有機化合物、以硫為主的無機化合物及含硫聚合物。較佳地,使用元素硫。
固體導電材料可為任何適當的導電材料。較佳地,此固體導電材料可由碳形成。例子包括碳黑、碳纖維及奈米碳管。其他適合材料包括金屬(例如薄片、屑及粉末)及導電聚合物。較佳地,採用碳黑。
電活性硫材料(例如元素硫)相對於導電材料(例如碳)的重量比為1到30:1;較佳地為2到8:1,更佳地為5到7:1。
電活性硫材料及導電材料的混合物可為一顆粒
狀混合物。此混合物可具有50奈米至20微米之平均粒子大小,較佳地為100奈米至5微米。
電活性硫材料及導電材料的混合物(亦即為電活性層)可選擇性地包括一黏合劑。適合的黏合劑可由例如下述物質中至少一者形成:聚氧乙烯、聚四氟乙烯、聚偏二氟乙烯、乙烯-丙烯-二烯橡膠、甲基丙烯酸酯(例如紫外光可固化甲基丙烯酸酯)和二乙烯基酯(例如熱可固化二乙烯基酯)。
如上所討論,電化學電池的陰極可進一步包含與電活性硫材料及固體導電材料之混合物接觸的集電器。例如,將電活性硫材料及固體導電材料之混合物沉積在集電器上。分隔件亦設置於電化學電池之陽極和陰極之間。例如,分隔件可與電活性硫材料及固體導電材料之混合物接觸,接著與集電器接觸。
適合的集電器包括金屬基材,如金屬或金屬合金形成的箔、片或網。在一較佳的實施例中,集電器為鋁箔。
分隔件可為允許離子在電池電極間移動的任何適當之多孔性基材。基材的孔洞率應至少30%,較佳地至少為50%,例如,在60%以上。適當之分隔件包括聚合物材料形成之網狀物。適當的聚合物包括聚丙烯、尼龍和聚乙烯。特佳為非織聚丙烯。有可能應用多層分隔件。
較佳地,此電解質包含至少一鋰鹽及至少一有機溶劑。適當的鋰鹽包括下述中至少一者:六氟磷酸鋰(LiPF6)、六氟砷酸鋰(LiAsF6)、過氯酸鋰(LiClO4)、雙三氟
甲基磺醯亞胺鋰(LiN(CF3SO2)2)、氟硼酸鋰及三氟甲基磺酸鋰(CF3SO3Li)。較佳地,此鋰鹽為三氟甲基磺酸鋰。
適當的有機溶劑為四氫呋喃、2-甲基四氫呋喃、碳酸二甲酯、碳酸二乙酯、碳酸甲乙酯、碳酸甲丙酯、丙基丙酸甲酯、丙基丙酸乙酯、乙酸甲酯、二甲氧基乙烷、1,3-二氧戊環、二甘醇二甲醚(二乙二醇二甲醚)、四乙二醇二甲醚、碳酸亞乙酯、碳酸亞丙酯、γ-丁內酯、二氧戊環、六甲基磷醯胺、吡啶、二甲亞碸、磷酸三丁酯、磷酸三甲基、N,N,N,N-四乙基磺醯胺和碸及其等之混合物。較佳地,此有機溶劑為碸及碸之混合物。碸的例子是二甲碸及環丁碸。環丁碸可作為唯一溶劑或與例如其他碸組合應用。
用於電解質之有機溶劑應能夠溶解例如具有化學式Sn 2-的多硫化種類類,其中n=2到12,該等多硫化種類形成於當電池放電期間電活性硫材料還原時。
電解質中之鋰鹽濃度較佳為0.1到5M,更佳地為0.5到3M,例如1M。鋰鹽較佳的存在濃度為至少70%飽和度,較佳地為至少80%飽和度,更佳地為至少90%飽和度,例如95%到99%飽和度。
在一實施例中,電解質包含三氟甲基磺酸鋰及環丁碸。
電解質相對於電活性硫材料與導電材料之總量的重重比為1-15:1,較佳地為2-9:1,更佳地為6-8:1。
圖1描繪出依據比較方法來循環鋰硫電池之充電
-放電曲線。
圖2描繪依據本發明方法之實施例來循環之鋰硫電池的充電-放電曲線。
圖3描繪出依據比較方法來循環鋰硫電池之充電-放電曲線。
圖4描繪出依據比較方法來循環鋰硫電池之充電-放電曲線。
圖5描繪依據本發明方法之實施例來循環之鋰硫電池的充電-放電曲線。
圖6描繪依據本發明方法之實施例來循環之鋰硫電池的充電-放電曲線。
圖7描繪依據本發明方法之實施例來循環之鋰硫電池的充電-放電曲線。
圖8描繪依據本發明方法之實施例來循環之鋰硫電池的充電-放電曲線。
圖9描繪出依據比較方法來循環鋰硫電池之充電-放電曲線。
圖1描繪出藉由充電至固定電壓2.45V及放電至固定電壓1.5V來循環的鋰硫電池之充電-放電曲線。
圖2描繪出依據本發明之一實施例藉由充電(不足)至2.33V及放電(不足)至1.75V來循環鋰硫電池之充電-放電曲線。二種電池是以相同方式製造成相同之規格。由
圖式中可看出,藉由根據本發明循環電池可降低電容消退的速率。
在以下實施例中,使用具有約2.45V的OCV(開路電壓)的實質相同鋰-硫袋電池。
使每個電池接受預循環方法處理,其涉及使用1.5-2.45V之電壓範圍,基於70%的理論電容,以C/5放電電池,接著分別以C/5之放電及C/10之充電進行3個充電/放電循環。
所有充電/放電半循環皆分別以C/10及C/5速率進行。
測試下列的放電一充電電壓:1.75V到2.45V(圖3)
1.95V到2.45V(圖4)
1.5V到2.4V(圖5)
1.95V到2.4V(圖6)
1.5V到2.33V(圖7)
1.75V到2.33V(圖8)
1.75V到2.25V(圖9)
由圖5、6、7及8與圖3、4及9的比較可看出,藉由根據本發明循環電池,降低電容消退速率。特別地,藉由充電電池至2.33V,觀察到循環壽命的明顯改良。當電池完全充電至2.45V(參見圖3及4)或不足充電至2.25V(參見圖9)時,無法達到此等改善。
Claims (14)
- 一種循環鋰硫電池之方法,該方法包含:(i)放電鋰硫電池(ii)當該電池的電壓達到1.5到2.1V範圍內的閾值放電電壓時終止放電,(iii)充電該鋰硫電池,以及(iv)當電池電壓達到2.3到2.4V範圍內的閾值充電電壓時終止充電,其中該鋰硫電池在閾值充電電壓時未完全充電,以及其中該鋰硫電池在閾值放電電壓時未完全放電。
- 如請求項2之方法,其中該閾值放電電壓約1.75V。
- 如請求項1或2之方法,其中該閾值充電電壓約2.33V。
- 如前述請求項中任一項之方法,其中重覆步驟(i)至(iv)至少2個放電-充電循環。
- 如請求項4之方法,其中重覆步驟(i)至(iv)至少20個放電-充電循環。
- 如前述請求項中任一項之方法,其中當至少80%的該陰極硫材料溶解於該電解質時,發生終止充電及放電的點。
- 一種用於控制鋰硫電池放電及充電之電池組管理系統,該系統包含: 用於在高於該電池完全放電狀態下的電池電壓的閾值放電電壓下,終止該鋰硫電池放電的裝置,用於充電該鋰硫電池之裝置,以及用於在低於該電池完全充電狀態下的電池電壓的閾值充電電壓下,終止該鋰硫電池充電的裝置。
- 如請求項7之系統,其包含用於在充電及放電期間監測該電池之電壓的裝置。
- 如請求項7或8之系統,其中該用以終止電池放電的裝置,在當電池電壓為1.7V到1.8V時終止放電。
- 如請求項9之系統,其中該用於終止電池放電的裝置,在當該電池的電壓為約1.75V時終止放電。
- 如請求項7至10中任一項之系統,其中該用於終止電池充電的裝置,在當該電池的電壓為2.3V到2.4V時終止充電。
- 如請求項11之系統,其中該用於終止電池充電的裝置,在當該電池的電壓為約2.33V時終止充電。
- 如請求項7至12中任一項之系統,其額外地包括用於耦合該系統至一鋰硫電池組的裝置。
- 如請求項13之系統,其包含一鋰硫電池組。
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??1321703.9 | 2013-12-09 | ||
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Families Citing this family (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US10033213B2 (en) * | 2014-09-30 | 2018-07-24 | Johnson Controls Technology Company | Short circuit wake-up system and method for automotive battery while in key-off position |
US11784303B2 (en) | 2015-09-22 | 2023-10-10 | Ii-Vi Delaware, Inc. | Immobilized chalcogen and use thereof in a rechargeable battery |
US11588149B2 (en) | 2015-09-22 | 2023-02-21 | Ii-Vi Delaware, Inc. | Immobilized selenium in a porous carbon with the presence of oxygen, a method of making, and uses of immobilized selenium in a rechargeable battery |
US10734638B2 (en) * | 2015-09-22 | 2020-08-04 | Ii-Vi Delaware, Inc. | Immobilized selenium, a method of making, and uses of immobilized selenium in a rechargeable battery |
CN106159361B (zh) * | 2016-09-30 | 2018-12-04 | 上海空间电源研究所 | 一种锂硫电池充电方法 |
US11870059B2 (en) | 2017-02-16 | 2024-01-09 | Consejo Superior De Investigaciones Cientificas (Csic) | Immobilized selenium in a porous carbon with the presence of oxygen, a method of making, and uses of immobilized selenium in a rechargeable battery |
WO2019022399A2 (ko) * | 2017-07-26 | 2019-01-31 | 주식회사 엘지화학 | 리튬-황 전지의 수명 개선 방법 |
KR102229455B1 (ko) * | 2017-07-26 | 2021-03-18 | 주식회사 엘지화학 | 리튬-황 전지의 수명 개선 방법 |
CN109616705A (zh) * | 2018-11-26 | 2019-04-12 | 上海大学 | 提高锂离子电池容量的方法 |
JP7202977B2 (ja) * | 2019-06-11 | 2023-01-12 | 日産自動車株式会社 | リチウム二次電池の制御方法および制御装置、並びにリチウム二次電池システム |
US11688895B1 (en) | 2022-03-10 | 2023-06-27 | Lyten, Inc. | Battery safety system for detecting analytes |
Family Cites Families (170)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3030720A (en) | 1960-06-08 | 1962-04-24 | Highland Supply Corp | Portable collapsible artificial christmas trees |
US3185590A (en) | 1961-01-06 | 1965-05-25 | North American Aviation Inc | Lightweight secondary battery |
US3578500A (en) | 1968-07-08 | 1971-05-11 | American Cyanamid Co | Nonaqueous electro-chemical current producing cell having soluble cathode depolarizer |
US3639174A (en) | 1970-04-22 | 1972-02-01 | Du Pont | Voltaic cells with lithium-aluminum alloy anode and nonaqueous solvent electrolyte system |
US3721113A (en) | 1971-08-23 | 1973-03-20 | Du Pont | Rolling of lithium |
US3907591A (en) | 1971-12-30 | 1975-09-23 | Varta Ag | Positive sulphur electrode for galvanic cells and method of producing the same |
US3951688A (en) | 1972-04-17 | 1976-04-20 | The Gates Rubber Company | Method and apparatus for pasting battery plates |
US3778310A (en) | 1972-05-01 | 1973-12-11 | Du Pont | High energy density battery having unsaturated heterocyclic solvent containing electrolyte |
US3877983A (en) | 1973-05-14 | 1975-04-15 | Du Pont | Thin film polymer-bonded cathode |
US3907597A (en) | 1974-09-27 | 1975-09-23 | Union Carbide Corp | Nonaqueous cell having an electrolyte containing sulfolane or an alkyl-substituted derivative thereof |
US4048389A (en) | 1976-02-18 | 1977-09-13 | Union Carbide Corporation | Cathode or cathode collector arcuate bodies for use in various cell systems |
US4060674A (en) | 1976-12-14 | 1977-11-29 | Exxon Research And Engineering Company | Alkali metal anode-containing cells having electrolytes of organometallic-alkali metal salts and organic solvents |
US4104451A (en) | 1977-09-26 | 1978-08-01 | Exxon Research & Engineering Co. | Alkali metal anode/chalcogenide cathode reversible batteries having alkali metal polyaryl metallic compound electrolytes |
US4118550A (en) | 1977-09-26 | 1978-10-03 | Eic Corporation | Aprotic solvent electrolytes and batteries using same |
US4163829A (en) | 1977-11-14 | 1979-08-07 | Union Carbide Corporation | Metallic reducing additives for solid cathodes for use in nonaqueous cells |
FR2442512A1 (fr) | 1978-11-22 | 1980-06-20 | Anvar | Nouveaux materiaux elastomeres a conduction ionique |
US4218523A (en) | 1979-02-28 | 1980-08-19 | Union Carbide Corporation | Nonaqueous electrochemical cell |
US4252876A (en) | 1979-07-02 | 1981-02-24 | Eic Corporation | Lithium battery |
US4318430A (en) | 1979-11-07 | 1982-03-09 | General Electric Company | Apparatus for making rechargeable electrodes for electrochemical cells |
IL63207A (en) | 1980-07-24 | 1985-09-29 | Lonza Ag | Process for the preparation of 2-(2-aminothiazole-4-yl)-2-(syn)-methoxyiminoacetic acid esters |
IL61085A (en) | 1980-09-19 | 1983-07-31 | Univ Ramot | Nonaqueous sulfur cell |
JPS59194361A (ja) | 1983-03-18 | 1984-11-05 | Toshiba Battery Co Ltd | 空気電池 |
US4499161A (en) | 1983-04-25 | 1985-02-12 | Eic Laboratories, Inc. | Electrochemical cell using dimethoxymethane and/or trimethoxymethane as solvent for electrolyte |
US4550064A (en) | 1983-12-08 | 1985-10-29 | California Institute Of Technology | High cycle life secondary lithium battery |
FR2576712B1 (fr) | 1985-01-30 | 1988-07-08 | Accumulateurs Fixes | Generateur electrochimique a electrolyte non aqueux |
DE3687804T2 (de) | 1985-07-05 | 1993-09-23 | Showa Denko Kk | Sekundaerbatterie. |
US4725927A (en) | 1986-04-08 | 1988-02-16 | Asahi Glass Company Ltd. | Electric double layer capacitor |
JPH0752647B2 (ja) | 1986-09-26 | 1995-06-05 | 松下電器産業株式会社 | 電池用電極とその製造方法 |
GB8630857D0 (en) | 1986-12-24 | 1987-02-04 | Sylva Ind Ltd | Electrical contact tab |
JPH01124969A (ja) | 1987-11-10 | 1989-05-17 | Hitachi Maxell Ltd | リチウム二次電池 |
CA2016777C (en) | 1989-05-16 | 1993-10-12 | Norio Takami | Nonaqueous electrolyte secondary battery |
US5219684A (en) | 1990-05-16 | 1993-06-15 | Her Majesty The Queen In Right Of Canada, As Represented By The Province Of British Columbia | Electrochemical cells containing a safety electrolyte solvent |
US5368958A (en) | 1992-08-20 | 1994-11-29 | Advanced Energy Technologies Incorporated | Lithium anode with conductive for and anode tab for rechargeable lithium battery |
US5587253A (en) | 1993-03-05 | 1996-12-24 | Bell Communications Research, Inc. | Low resistance rechargeable lithium-ion battery |
US5460905A (en) | 1993-06-16 | 1995-10-24 | Moltech Corporation | High capacity cathodes for secondary cells |
US5961672A (en) | 1994-02-16 | 1999-10-05 | Moltech Corporation | Stabilized anode for lithium-polymer batteries |
US5648187A (en) | 1994-02-16 | 1997-07-15 | Moltech Corporation | Stabilized anode for lithium-polymer batteries |
JPH0869812A (ja) | 1994-08-30 | 1996-03-12 | Shin Kobe Electric Mach Co Ltd | 密閉形鉛蓄電池およびその製造法 |
JPH08138650A (ja) | 1994-11-01 | 1996-05-31 | Dainippon Ink & Chem Inc | 非水電解液二次電池用炭素質電極板および二次電池 |
JP3385115B2 (ja) | 1994-11-02 | 2003-03-10 | 松下電器産業株式会社 | ゲル電解質およびリチウム二次電池 |
US6020089A (en) | 1994-11-07 | 2000-02-01 | Sumitomo Electric Industries, Ltd. | Electrode plate for battery |
US5814420A (en) | 1994-11-23 | 1998-09-29 | Polyplus Battery Company, Inc. | Rechargeable positive electrodes |
US5523179A (en) | 1994-11-23 | 1996-06-04 | Polyplus Battery Company | Rechargeable positive electrode |
US5686201A (en) | 1994-11-23 | 1997-11-11 | Polyplus Battery Company, Inc. | Rechargeable positive electrodes |
US6358643B1 (en) | 1994-11-23 | 2002-03-19 | Polyplus Battery Company | Liquid electrolyte lithium-sulfur batteries |
US5582623A (en) | 1994-11-23 | 1996-12-10 | Polyplus Battery Company, Inc. | Methods of fabricating rechargeable positive electrodes |
US6030720A (en) | 1994-11-23 | 2000-02-29 | Polyplus Battery Co., Inc. | Liquid electrolyte lithium-sulfur batteries |
US6376123B1 (en) | 1994-11-23 | 2002-04-23 | Polyplus Battery Company | Rechargeable positive electrodes |
US5848351A (en) | 1995-04-03 | 1998-12-08 | Mitsubishi Materials Corporation | Porous metallic material having high specific surface area, method of producing the same, porous metallic plate material and electrode for alkaline secondary battery |
JPH08298230A (ja) | 1995-04-26 | 1996-11-12 | Mitsubishi Chem Corp | 電気二重層コンデンサ用電解液 |
JPH08298229A (ja) | 1995-04-26 | 1996-11-12 | Mitsubishi Chem Corp | 電気二重層コンデンサ用電解液 |
US5529860A (en) | 1995-06-07 | 1996-06-25 | Moltech Corporation | Electroactive high storage capacity polyacetylene-co-polysulfur materials and electrolytic cells containing same |
US5744262A (en) | 1995-06-07 | 1998-04-28 | Industrial Technology Research Institute | Stable high-voltage electrolyte for lithium secondary battery |
WO1996041388A1 (en) | 1995-06-07 | 1996-12-19 | Moltech Corporation | Electroactive high storage capacity polyacetylene-co-polysulfur materials and electrolytic cells containing same |
JPH0927328A (ja) | 1995-07-10 | 1997-01-28 | Asahi Denka Kogyo Kk | 非水電池 |
JPH09147913A (ja) | 1995-11-22 | 1997-06-06 | Sanyo Electric Co Ltd | 非水電解質電池 |
US5797428A (en) | 1996-01-11 | 1998-08-25 | Vemco Corporation | Pop-alert device |
US5919587A (en) | 1996-05-22 | 1999-07-06 | Moltech Corporation | Composite cathodes, electrochemical cells comprising novel composite cathodes, and processes for fabricating same |
EP0910874B1 (en) | 1996-06-14 | 2001-11-21 | Moltech Corporation | Composition useful in elctrolytes of secondary battery cells |
JPH10284076A (ja) | 1997-04-01 | 1998-10-23 | Matsushita Electric Ind Co Ltd | アルカリ蓄電池及びその電極の製造方法 |
KR100368753B1 (ko) | 1997-06-27 | 2003-04-08 | 주식회사 엘지화학 | 리튬전지용음극및그의제조방법 |
US20020168574A1 (en) | 1997-06-27 | 2002-11-14 | Soon-Ho Ahn | Lithium ion secondary battery and manufacturing method of the same |
US6090504A (en) | 1997-09-24 | 2000-07-18 | Korea Kumho Petrochemical Co., Ltd. | High capacity composite electrode and secondary cell therefrom |
WO1999019932A1 (en) | 1997-10-15 | 1999-04-22 | Moltech Corporation | Non-aqueous electrolyte solvents for secondary cells |
US6162562A (en) | 1997-10-28 | 2000-12-19 | Pioneer Electronic Corporation | Secondary cell comprising a positive electrode containing polyaniline and 4 diazo compound |
US6201100B1 (en) | 1997-12-19 | 2001-03-13 | Moltech Corporation | Electroactive, energy-storing, highly crosslinked, polysulfide-containing organic polymers and methods for making same |
US6210831B1 (en) | 1997-12-19 | 2001-04-03 | Moltech Corporation | Cathodes comprising electroactive sulfur materials and secondary batteries using same |
DE69813164T2 (de) | 1997-12-22 | 2003-10-23 | Japan Storage Battery Co Ltd | Verfahren zur Herstellung einer porösen, mit aktiver Masse gefüllten Elektrode |
JPH11273729A (ja) | 1998-03-19 | 1999-10-08 | Yazaki Corp | リチウム塩及びスルフィド系二次電池 |
US6350545B2 (en) | 1998-08-25 | 2002-02-26 | 3M Innovative Properties Company | Sulfonylimide compounds |
JP4016506B2 (ja) | 1998-10-16 | 2007-12-05 | ソニー株式会社 | 固体電解質電池 |
US6302928B1 (en) | 1998-12-17 | 2001-10-16 | Moltech Corporation | Electrochemical cells with high volumetric density of electroactive sulfur-containing materials in cathode active layers |
JP3573992B2 (ja) | 1999-02-15 | 2004-10-06 | 三洋電機株式会社 | リチウム二次電池 |
KR100322449B1 (ko) | 1999-06-07 | 2002-02-07 | 김순택 | 리튬 이차 전지용 전해액 및 이를 사용한 리튬 이차 전지 |
JP3754239B2 (ja) * | 1999-07-27 | 2006-03-08 | 三洋電機株式会社 | 電池の充放電制御方法 |
US6413284B1 (en) | 1999-11-01 | 2002-07-02 | Polyplus Battery Company | Encapsulated lithium alloy electrodes having barrier layers |
WO2001036206A1 (en) | 1999-11-12 | 2001-05-25 | Fargo Electronics, Inc. | Thermal printhead compensation |
US6733924B1 (en) | 1999-11-23 | 2004-05-11 | Moltech Corporation | Lithium anodes for electrochemical cells |
US6797428B1 (en) | 1999-11-23 | 2004-09-28 | Moltech Corporation | Lithium anodes for electrochemical cells |
US7247408B2 (en) | 1999-11-23 | 2007-07-24 | Sion Power Corporation | Lithium anodes for electrochemical cells |
JP4797219B2 (ja) | 1999-12-09 | 2011-10-19 | パナソニック株式会社 | 電池のリード線接続装置 |
US6329789B1 (en) * | 1999-12-21 | 2001-12-11 | Moltech Corporation | Methods of charging lithium-sulfur batteries |
EP1202374A4 (en) | 2000-03-28 | 2009-05-27 | Ngk Insulators Ltd | LITHIUM ACCUMULATOR |
US6344293B1 (en) | 2000-04-18 | 2002-02-05 | Moltech Corporation | Lithium electrochemical cells with enhanced cycle life |
CN1182617C (zh) | 2000-05-08 | 2004-12-29 | 森陶硝子株式会社 | 电解质、包含电解质的离子导体和包括这种离子导体的电化学装置 |
WO2001097304A1 (en) | 2000-06-12 | 2001-12-20 | Korea Institute Of Science And Technology | Multi-layered lithium electrode, its preparation and lithium batteries comprising it |
KR100756812B1 (ko) | 2000-07-17 | 2007-09-07 | 마츠시타 덴끼 산교 가부시키가이샤 | 비수 전기화학 장치 |
KR100326466B1 (ko) | 2000-07-25 | 2002-02-28 | 김순택 | 리튬 설퍼 전지용 전해액 |
KR100326467B1 (ko) | 2000-07-25 | 2002-02-28 | 김순택 | 리튬 설퍼 전지용 전해액 |
JP2002075446A (ja) | 2000-08-02 | 2002-03-15 | Samsung Sdi Co Ltd | リチウム−硫黄電池 |
US6544691B1 (en) | 2000-10-11 | 2003-04-08 | Sandia Corporation | Batteries using molten salt electrolyte |
WO2002050933A2 (en) | 2000-12-21 | 2002-06-27 | Moltech Corporation | Lithium anodes for electrochemical cells |
US6632573B1 (en) | 2001-02-20 | 2003-10-14 | Polyplus Battery Company | Electrolytes with strong oxidizing additives for lithium/sulfur batteries |
KR100417088B1 (ko) | 2001-05-22 | 2004-02-05 | 주식회사 엘지화학 | 안전성을 향상시키는 비수전해액 첨가제 및 이를 포함하는비수전해액 리튬이온 2차 전지 |
US7217477B2 (en) | 2001-05-22 | 2007-05-15 | Lg Chem, Ltd. | Non-aqueous electrolyte additive for improving safety and lithium ion secondary battery comprising the same |
KR100385357B1 (ko) | 2001-06-01 | 2003-05-27 | 삼성에스디아이 주식회사 | 리튬-황 전지 |
CA2451634C (en) | 2001-06-29 | 2009-06-30 | Kanebo, Limited | Organic electrolytic capacitor |
CN100595964C (zh) | 2001-07-27 | 2010-03-24 | 麻省理工学院 | 电池结构、自组织结构及相关方法 |
US7241535B2 (en) | 2001-10-15 | 2007-07-10 | Samsung Sdi Co., Ltd. | Electrolyte for lithium-sulfur batteries and lithium-sulfur batteries comprising the same |
KR100466924B1 (ko) | 2001-12-28 | 2005-01-24 | 한국과학기술원 | 액적화학증착법을 이용한 초박막형 리튬이온 2차전지의제조방법 |
US6893762B2 (en) | 2002-01-16 | 2005-05-17 | Alberta Research Council, Inc. | Metal-supported tubular micro-fuel cell |
CA2424561A1 (en) | 2002-04-02 | 2003-10-02 | Nippon Shokubai Co., Ltd. | Material for electrolytic solutions and use thereof |
CA2384215A1 (en) | 2002-04-30 | 2003-10-30 | Richard Laliberte | Electrochemical bundle and method for making same |
KR100463181B1 (ko) * | 2002-07-12 | 2004-12-23 | 삼성에스디아이 주식회사 | 리튬-설퍼 전지용 전해액 및 이를 포함하는 리튬-설퍼 전지 |
DE10238943B4 (de) | 2002-08-24 | 2013-01-03 | Evonik Degussa Gmbh | Separator-Elektroden-Einheit für Lithium-Ionen-Batterien, Verfahren zu deren Herstellung und Verwendung in Lithium-Batterien sowie eine Batterie, aufweisend die Separator-Elektroden-Einheit |
KR100467456B1 (ko) | 2002-09-10 | 2005-01-24 | 삼성에스디아이 주식회사 | 리튬-황 전지용 전해액 및 이를 포함하는 리튬-황 전지 |
KR100467453B1 (ko) | 2002-09-12 | 2005-01-24 | 삼성에스디아이 주식회사 | 리튬 이차 전지용 전해액 및 이를 포함하는 리튬 이차 전지 |
KR100449765B1 (ko) | 2002-10-12 | 2004-09-22 | 삼성에스디아이 주식회사 | 리튬전지용 리튬메탈 애노드 |
KR100467436B1 (ko) | 2002-10-18 | 2005-01-24 | 삼성에스디아이 주식회사 | 리튬-황 전지용 음극, 그의 제조 방법 및 그를 포함하는리튬-황 전지 |
KR100477969B1 (ko) | 2002-10-25 | 2005-03-23 | 삼성에스디아이 주식회사 | 리튬 전지용 음극 및 이를 포함하는 리튬 전지 |
KR100485093B1 (ko) | 2002-10-28 | 2005-04-22 | 삼성에스디아이 주식회사 | 리튬-황 전지용 양극 및 이를 포함하는 리튬-황 전지 |
KR100472513B1 (ko) | 2002-11-16 | 2005-03-11 | 삼성에스디아이 주식회사 | 리튬 설퍼 전지용 유기 전해액 및 이를 채용한 리튬 설퍼전지 |
KR100875112B1 (ko) | 2002-11-16 | 2008-12-22 | 삼성에스디아이 주식회사 | 비수계 전해액 및 이를 채용한 리튬 전지 |
KR100477751B1 (ko) | 2002-11-16 | 2005-03-21 | 삼성에스디아이 주식회사 | 비수계 전해액 및 이를 채용한 리튬 전지 |
JP2004179160A (ja) | 2002-11-26 | 2004-06-24 | Samsung Sdi Co Ltd | リチウム−硫黄電池用正極 |
US7108942B1 (en) | 2003-03-27 | 2006-09-19 | Wilson Greatbatch Technologies, Inc. | Efficient electrode assembly design for cells with alkali metal anodes |
US7488547B1 (en) | 2003-04-22 | 2009-02-10 | Benedetto Anthony Iacovelli | Fuel cell, components and systems |
JP4055642B2 (ja) | 2003-05-01 | 2008-03-05 | 日産自動車株式会社 | 高速充放電用電極および電池 |
US7245107B2 (en) * | 2003-05-09 | 2007-07-17 | Enerdel, Inc. | System and method for battery charge control based on a cycle life parameter |
JP4494731B2 (ja) | 2003-06-13 | 2010-06-30 | 三菱重工業株式会社 | 二次電池、二次電池の製造方法 |
KR100573109B1 (ko) | 2003-06-17 | 2006-04-24 | 삼성에스디아이 주식회사 | 유기 전해액 및 이를 채용한 리튬 전지 |
US7781106B2 (en) * | 2003-08-11 | 2010-08-24 | Ube Industries, Ltd. | Lithium secondary cell and its nonaqueous electrolyte |
JP2005071641A (ja) | 2003-08-27 | 2005-03-17 | Japan Storage Battery Co Ltd | 非水電解質二次電池およびその製造方法 |
US7335440B2 (en) | 2003-09-12 | 2008-02-26 | Medtronic, Inc. | Lithium-limited anode subassembly with solid anode current collector and spacer |
JP2005108724A (ja) | 2003-09-30 | 2005-04-21 | Sanyo Electric Co Ltd | 非水電解質二次電池 |
JP2005166536A (ja) | 2003-12-04 | 2005-06-23 | Sanyo Electric Co Ltd | 非水電解質二次電池 |
US7354680B2 (en) | 2004-01-06 | 2008-04-08 | Sion Power Corporation | Electrolytes for lithium sulfur cells |
US7019494B2 (en) * | 2004-01-06 | 2006-03-28 | Moltech Corporation | Methods of charging lithium sulfur cells |
US7646171B2 (en) | 2004-01-06 | 2010-01-12 | Sion Power Corporation | Methods of charging lithium sulfur cells |
JP4399779B2 (ja) | 2004-02-25 | 2010-01-20 | 株式会社豊田中央研究所 | 電解質粒子、正極、負極及びリチウム二次電池 |
US8334079B2 (en) | 2004-04-30 | 2012-12-18 | NanoCell Systems, Inc. | Metastable ceramic fuel cell and method of making the same |
US20060024579A1 (en) | 2004-07-27 | 2006-02-02 | Vladimir Kolosnitsyn | Battery electrode structure and method for manufacture thereof |
DE602005026547D1 (de) | 2004-10-29 | 2011-04-07 | Medtronic Inc | Verfahren zum aufladen einer lithiumionenbatterie |
JP4594039B2 (ja) | 2004-11-09 | 2010-12-08 | 本城金属株式会社 | 積層フィルム被覆リチウム箔 |
US20060105233A1 (en) | 2004-11-18 | 2006-05-18 | Hiroyuki Morita | Battery |
JP5466364B2 (ja) | 2004-12-02 | 2014-04-09 | オクシス・エナジー・リミテッド | リチウム・硫黄電池用電解質及びこれを使用するリチウム・硫黄電池 |
GB2422244B (en) * | 2005-01-18 | 2007-01-10 | Intellikraft Ltd | Improvements relating to electrolyte compositions for batteries using sulphur or sulphur compounds |
KR101353363B1 (ko) | 2005-01-18 | 2014-02-18 | 옥시스 에너지 리미티드 | 황 또는 황 화합물을 사용한 전지용 전해질 조성물에 관한개선 |
US7183734B2 (en) * | 2005-02-18 | 2007-02-27 | Atmel Corporation | Sensorless control of two-phase brushless DC motor |
KR100813240B1 (ko) | 2005-02-18 | 2008-03-13 | 삼성에스디아이 주식회사 | 유기 전해액 및 이를 채용한 리튬 전지 |
RU2402842C2 (ru) | 2005-03-22 | 2010-10-27 | Оксис Энерджи Лимитед | Химический источник электроэнергии и способ его изготовления |
EP1865520B1 (en) | 2005-03-31 | 2013-06-05 | Fuji Jukogyo Kabushiki Kaisha | Lithium ion capacitor |
US7688075B2 (en) * | 2005-04-20 | 2010-03-30 | Sion Power Corporation | Lithium sulfur rechargeable battery fuel gauge systems and methods |
KR100803191B1 (ko) | 2005-06-24 | 2008-02-14 | 삼성에스디아이 주식회사 | 유기 전해액 및 이를 채용한 리튬 전지 |
WO2007034243A1 (en) | 2005-09-26 | 2007-03-29 | Oxis Energy Limited | Lithium-sulphur battery with high specific energy |
JP4842633B2 (ja) | 2005-12-22 | 2011-12-21 | 富士重工業株式会社 | 電池又はキャパシタ用リチウム金属箔の製造方法 |
KR100907623B1 (ko) | 2006-05-15 | 2009-07-15 | 주식회사 엘지화학 | 신규한 적층 구조의 이차전지용 전극조립체 |
GB2438890B (en) | 2006-06-05 | 2011-01-12 | Oxis Energy Ltd | Lithium secondary battery for operation over a wide range of temperatures |
JP4898308B2 (ja) | 2006-06-07 | 2012-03-14 | パナソニック株式会社 | 充電回路、充電システム、及び充電方法 |
KR100888284B1 (ko) | 2006-07-24 | 2009-03-10 | 주식회사 엘지화학 | 탭-리드 결합부의 전극간 저항차를 최소화한 전극조립체 및이를 포함하고 있는 전기화학 셀 |
GB0615870D0 (en) | 2006-08-10 | 2006-09-20 | Oxis Energy Ltd | An electrolyte for batteries with a metal lithium electrode |
JP5114036B2 (ja) | 2006-09-08 | 2013-01-09 | Necエナジーデバイス株式会社 | 積層型電池の製造方法 |
JP5297383B2 (ja) | 2006-10-25 | 2013-09-25 | オクシス・エナジー・リミテッド | 高比エネルギーのリチウム−硫黄電池及びその動作法 |
KR101342509B1 (ko) | 2007-02-26 | 2013-12-17 | 삼성에스디아이 주식회사 | 리튬 이차 전지 |
US8734986B2 (en) | 2007-07-11 | 2014-05-27 | Nissan Motor Co., Ltd. | Laminate type battery |
JP5111991B2 (ja) | 2007-09-28 | 2013-01-09 | 株式会社東芝 | 電池 |
KR101386165B1 (ko) | 2007-10-26 | 2014-04-17 | 삼성에스디아이 주식회사 | 실란계 화합물을 채용한 유기전해액 및 리튬 전지 |
JP4561859B2 (ja) | 2008-04-01 | 2010-10-13 | トヨタ自動車株式会社 | 二次電池システム |
GB0808059D0 (en) | 2008-05-02 | 2008-06-11 | Oxis Energy Ltd | Rechargeable battery with negative lithium electrode |
JP2013503439A (ja) | 2009-08-28 | 2013-01-31 | シオン・パワー・コーポレーション | 硫黄含有多孔質構造体を有する電気化学電池 |
KR20110024707A (ko) * | 2009-09-03 | 2011-03-09 | 주식회사 엘지화학 | 리튬 이차 전지의 충전 방법 |
JP5487895B2 (ja) | 2009-11-17 | 2014-05-14 | トヨタ自動車株式会社 | 集電体及びその製造方法 |
JP5397533B2 (ja) | 2010-02-22 | 2014-01-22 | トヨタ自動車株式会社 | 非水電解液型二次電池及び非水電解液型二次電池用非水電解液 |
JP2011192574A (ja) | 2010-03-16 | 2011-09-29 | Panasonic Corp | リチウム一次電池 |
WO2012049965A1 (ja) * | 2010-10-15 | 2012-04-19 | 三洋電機株式会社 | 電力管理システム |
JP4988974B2 (ja) | 2010-11-25 | 2012-08-01 | パナソニック株式会社 | 充電制御回路、電池駆動機器、充電装置及び充電方法 |
JP2013042598A (ja) * | 2011-08-16 | 2013-02-28 | Sanyo Electric Co Ltd | 充放電制御装置 |
CN103427125B (zh) * | 2012-05-15 | 2016-04-13 | 清华大学 | 硫基聚合物锂离子电池的循环方法 |
JP6219273B2 (ja) | 2012-05-22 | 2017-10-25 | 三洋電機株式会社 | リチウム二次電池用負極、リチウム二次電池、及びリチウム二次電池用負極の製造方法 |
FR2991104B1 (fr) * | 2012-05-23 | 2014-11-21 | Peugeot Citroen Automobiles Sa | Procede et dispositif pour la desulfatation d'une batterie |
-
2013
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- 2013-12-09 GB GB1321703.9A patent/GB2512424B/en active Active
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EP3614467A1 (en) | 2020-02-26 |
EP2784850A1 (en) | 2014-10-01 |
US20160006084A1 (en) | 2016-01-07 |
TWI635643B (zh) | 2018-09-11 |
US9935343B2 (en) | 2018-04-03 |
GB2512424A (en) | 2014-10-01 |
EP2979318A1 (en) | 2016-02-03 |
CN105229827A (zh) | 2016-01-06 |
KR102164616B1 (ko) | 2020-10-12 |
HK1197705A1 (zh) | 2015-02-06 |
CA2903944A1 (en) | 2014-10-02 |
RU2015145466A (ru) | 2017-05-17 |
JP6450997B2 (ja) | 2019-01-16 |
GB201321703D0 (en) | 2014-01-22 |
GB2512424B (en) | 2015-03-04 |
CA2903944C (en) | 2022-07-12 |
JP2016514884A (ja) | 2016-05-23 |
KR20150133733A (ko) | 2015-11-30 |
WO2014155069A1 (en) | 2014-10-02 |
RU2641667C2 (ru) | 2018-01-19 |
CN105229827B (zh) | 2018-10-09 |
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