DE19917000A1 - Primary lithium ion cell, especially button cell, has positive electrode active material comprising PTFE - Google Patents
Primary lithium ion cell, especially button cell, has positive electrode active material comprising PTFEInfo
- Publication number
- DE19917000A1 DE19917000A1 DE19917000A DE19917000A DE19917000A1 DE 19917000 A1 DE19917000 A1 DE 19917000A1 DE 19917000 A DE19917000 A DE 19917000A DE 19917000 A DE19917000 A DE 19917000A DE 19917000 A1 DE19917000 A1 DE 19917000A1
- Authority
- DE
- Germany
- Prior art keywords
- lithium
- positive electrode
- active material
- cell
- ptfe
- 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.)
- Withdrawn
Links
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 13
- 229920001343 polytetrafluoroethylene Polymers 0.000 title claims abstract description 12
- 239000004810 polytetrafluoroethylene Substances 0.000 title claims abstract description 12
- 239000007774 positive electrode material Substances 0.000 title 1
- -1 polytetrafluoroethylene Polymers 0.000 claims abstract description 9
- 239000011149 active material Substances 0.000 claims abstract description 7
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 5
- 229910000733 Li alloy Inorganic materials 0.000 claims abstract description 4
- 239000003792 electrolyte Substances 0.000 claims abstract description 4
- 239000001989 lithium alloy Substances 0.000 claims abstract description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 11
- 229940058401 polytetrafluoroethylene Drugs 0.000 claims description 10
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 239000004332 silver Substances 0.000 claims description 2
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000011888 foil Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 229910013870 LiPF 6 Inorganic materials 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 2
- QLOAVXSYZAJECW-UHFFFAOYSA-N methane;molecular fluorine Chemical class C.FF QLOAVXSYZAJECW-UHFFFAOYSA-N 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 1
- 229910015015 LiAsF 6 Inorganic materials 0.000 description 1
- 229910013063 LiBF 4 Inorganic materials 0.000 description 1
- 229910013684 LiClO 4 Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 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
- 229930188620 butyrolactone Natural products 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000003682 fluorination reaction Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011255 nonaqueous electrolyte Substances 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/04—Cells with aqueous electrolyte
- H01M6/06—Dry cells, i.e. cells wherein the electrolyte is rendered non-fluid
- H01M6/12—Dry cells, i.e. cells wherein the electrolyte is rendered non-fluid with flat electrodes
-
- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
-
- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
- H01M4/602—Polymers
- H01M4/604—Polymers containing aliphatic main chain polymers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/14—Cells with non-aqueous electrolyte
- H01M6/16—Cells with non-aqueous electrolyte with organic electrolyte
-
- 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
- H01M50/10—Primary casings; Jackets or wrappings
- H01M50/102—Primary casings; Jackets or wrappings characterised by their shape or physical structure
- H01M50/109—Primary casings; Jackets or wrappings characterised by their shape or physical structure of button or coin shape
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Primary Cells (AREA)
Abstract
Die Erfindung betrifft eine primäre Lithium-Ionen-Zelle, die mindestens eine negative Elektrode und mindestens eine durch einen Separator davon getrennte positive Elektrode sowie einen nichtwäßrigen Lithium-Ionen leitenden Elektrolyten in einem gasdichten Gehäuse besitzt, wobei das aktive Material der negativen Elektrode aus Lithiummetall oder einer Lithiumlegierung und das aktive Material der positiven Elektrode aus Polytetrafluorethylen besteht.The invention relates to a primary lithium-ion cell which has at least one negative electrode and at least one positive electrode separated by a separator and a non-aqueous lithium-ion-conducting electrolyte in a gas-tight housing, the active material of the negative electrode being made of lithium metal or a lithium alloy and the active material of the positive electrode consists of polytetrafluoroethylene.
Description
Die Erfindung betrifft eine primäre Lithium-Ionen-Zelle, die mindestens eine negative Elektro de und mindestens eine durch einen Separator davon getrennte positive Elektrode sowie einen nichtwäßrigen Lithium-Ionen leitenden Elektrolyten in einem gasdichten Gehäuse be sitzt, wobei das aktive Material der negativen Elektrode aus Lithiummetall oder einer Lithium legierung besteht.The invention relates to a primary lithium-ion cell, which has at least one negative electric de and at least one positive electrode separated therefrom by a separator and a non-aqueous lithium-ion conductive electrolyte in a gas-tight housing sits, the active material of the negative electrode made of lithium metal or a lithium alloy is made.
Aus den Dokumenten US 3,514,337, US 4,248,946, US 5,246,795 und EP-A 0 840 389 sind Lithium-Ionen-Zellen der vorgenannten Art bekannt. Das Lithiummetall oder die Lithiumlegie rung wird vorzugsweise auf ein metallisches Trägermaterial, wie Nickel-, Kupfer- oder Titan streckmetall, aufgebracht. Als Separatormaterial werden ein oder mehrschichtige poröse Polypropylen-, Polyethylen-Folien oder Glasfaservliese eingesetzt. Die nichtwäßrigen Elektrolyte sind vorzugsweise 1molare Lösungen von Lithiumsalzen wie LiPF6, LiAsF6, LiBF4 oder LiClO4 in Mischungen von cyclischen und linearen Carbonaten, wie Ethylen- (EC) oder Propylencarbonat (PC) und Diethyl- (DEC) oder Dimethylcarbonat (DMC), und cyclischen oder linearen Ketonen oder Ethern, wie beispielsweise Methylethylketon (MEK), Butyrolac ton oder Tetrahydrofuran (THF), dar. Die positiven Elektroden der bekannten Lithium-Ionen- Zellen bestehen aus fluorierten Kohlenstoffverbindungen (CnFx), die vorzugsweise durch Hochtemperaturfluorierung von Graphiten erhalten werden. Diese fluorierten Kohlenstoffver bindungen werden zusammen mit Leitmitteln wie Ruß-, Graphit-, Kupfer-, Nickel- oder Silberpulvern und Bindemitteln wie Polytetrafluorethylen (PTFE) zu Tabletten gepreßt und mit metallischen Ableitern wie Folien, Lochbleche, Streckmetallgitter, Netze oder Vliese aus Metallen wie Nickel, Aluminium oder Titan versehen.Lithium-ion cells of the aforementioned type are known from documents US Pat. No. 3,514,337, US Pat. No. 4,248,946, US Pat. No. 5,246,795 and EP-A 0 840 389. The lithium metal or lithium alloy is preferably applied to a metallic carrier material, such as nickel, copper or titanium expanded metal. One or multi-layer porous polypropylene, polyethylene foils or glass fiber fleeces are used as separator material. The non-aqueous electrolytes are preferably 1 molar solutions of lithium salts such as LiPF 6 , LiAsF 6 , LiBF 4 or LiClO 4 in mixtures of cyclic and linear carbonates such as ethylene (EC) or propylene carbonate (PC) and diethyl (DEC) or dimethyl carbonate (DMC ), and cyclic or linear ketones or ethers, such as methyl ethyl ketone (MEK), butyrolactone or tetrahydrofuran (THF). The positive electrodes of the known lithium-ion cells consist of fluorinated carbon compounds (C n F x ), which are preferably can be obtained by high temperature fluorination of graphites. These fluorinated carbon compounds are pressed together with conductive agents such as carbon black, graphite, copper, nickel or silver powders and binders such as polytetrafluoroethylene (PTFE) into tablets and with metallic conductors such as foils, perforated sheets, expanded metal grids, nets or nonwovens made of metals such as nickel , Aluminum or titanium.
Die Erfindung hat sich die Aufgabe gestellt, eine primäre Lithium-Ionen-Zelle anzugeben, die durch Verwendung eines neuen aktiven Materials für die positive Elektrode eine hohe Energiedichte besitzt.The object of the invention is to provide a primary lithium-ion cell which high by using a new active material for the positive electrode Owns energy density.
Erfindungsgemäß wird die Aufgabe durch die gattungsgemäß angegebene Lithium-Ionen- Zelle gelöst, welche die Merkmale des Anspruchs 1 aufweist.According to the invention, the object is specified by the generic lithium ion Solved cell, which has the features of claim 1.
Weitere vorzugsweise Ausgestaltungen der Erfindung und die bevorzugte Bauform für die erfindungsgemäßen Lithium-Ionen-Zellen sind in den Ansprüchen 2 bis 4 dargelegt.Further preferred embodiments of the invention and the preferred design for the Lithium-ion cells according to the invention are set out in claims 2 to 4.
Überraschenderweise wurde gefunden, daß das bisher nur als Bindemittel eingesetzte Poly
tetrafluorethylen (PTFE) als aktives Material in der positiven Elektrode dient. Dabei kann es
nicht nur die der Umsetzung gemäß der Reaktionsgleichung:
(C2F2)n + 4ne- → n (2 C + 4 F-)
Surprisingly, it was found that the poly tetrafluoroethylene (PTFE) previously used only as a binder serves as an active material in the positive electrode. It can not only be the implementation according to the reaction equation:
(C 2 F 2 ) n + 4ne - → n (2 C + 4 F - )
pro g PTFE die theoretisch errechnete spezifische Kapazität von 1072 mAh/g sondern je nach Entladebedingung sogar bis zu 1266 mAh/g erreichen.per g PTFE the theoretically calculated specific capacity of 1072 mAh / g but each can even reach up to 1266 mAh / g after the discharge condition.
Die Erfindung wird nachfolgend an Hand von zwei Beispielen und den damit erhaltenen Entladekurven näher erläutert.The invention is illustrated below with the aid of two examples and those obtained therewith Discharge curves explained in more detail.
Es zeigen:Show it:
Fig. 1 Die Entladekurve einer Knopfzelle, die dem Beispiel 1 entspricht und Fig. 1 The discharge curve of a button cell, which corresponds to Example 1 and
Fig. 2 Die Entladekurve einer Knopfzelle, die dem Beispiel 2 entspricht. Fig. 2 The discharge curve of a button cell, which corresponds to Example 2.
In einer Knopfzelle werden als negative Elektrode 5 Scheiben einer 0.25 mm dicken Lithium folie eingelegt. Als positive Elektrode wird ein 85 : 15 Gew.-% Gemisch aus Ni-Pulver und PTFE eingesetzt. Dazu werden 17 g Ni-Pulver und 3 g PTFE 15 Minuten gemischt und aus 250 mg bei einem Anpreßdruck von 15 kp/cm2 eine Elektrodentablette mit 2 cm2 Elektroden fläche gepreßt, die vor dem Einbau in das Knopfzellengehäuse über Nacht im Hochvakuum getrocknet wird. Als Separator wird ein Polypropylenylies (Celgard 3535; P334) verwendet. Der Elektrolyt besteht aus einer 1molaren Lösung von LiPF6 in einem aus EC/DMC/DEC bestehenden Lösemittelgemisch mit dem Volumenverhältnis 2/2/1. Bei der Entladung mit einem Entladestrom von 25 µA/cm2 bis zu einer Entladeschlußspannung von 0 V werden ca. 1250 mAh entladen.In a button cell, 5 slices of 0.25 mm thick lithium foil are inserted as a negative electrode. An 85: 15% by weight mixture of Ni powder and PTFE is used as the positive electrode. For this purpose, 17 g of Ni powder and 3 g of PTFE are mixed for 15 minutes and an electrode tablet with 2 cm 2 of electrode surface is pressed from 250 mg at a contact pressure of 15 kp / cm 2 , which is dried in a high vacuum overnight before being installed in the button cell housing . A polypropylene resin (Celgard 3535; P334) is used as the separator. The electrolyte consists of a 1 molar solution of LiPF 6 in a solvent mixture consisting of EC / DMC / DEC with a volume ratio of 2/2/1. When discharging with a discharge current of 25 µA / cm 2 up to a final discharge voltage of 0 V, approx. 1250 mAh are discharged.
Gemäß Beispiel 1 wird eine Knopfzelle hergestellt mit dem Unterschied, daß zur Herstellung der positiven Elektrodentablette ein 50 : 50 Gew.-% Gemisch von Ni-Pulver und PTFE einge setzt wird. Bei einer Entladung mit einem Entladestrom von 0,5 mA/cm2 bis zu einer Entlade schlußspannung von 0 V werden ca. 750 mAh entladen.According to Example 1, a button cell is produced with the difference that a 50:50% by weight mixture of Ni powder and PTFE is used to produce the positive electrode tablet. With a discharge with a discharge current of 0.5 mA / cm 2 up to a discharge voltage of 0 V approx. 750 mAh are discharged.
Claims (4)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19917000A DE19917000A1 (en) | 1999-04-15 | 1999-04-15 | Primary lithium ion cell, especially button cell, has positive electrode active material comprising PTFE |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19917000A DE19917000A1 (en) | 1999-04-15 | 1999-04-15 | Primary lithium ion cell, especially button cell, has positive electrode active material comprising PTFE |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE19917000A1 true DE19917000A1 (en) | 2000-10-19 |
Family
ID=7904647
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE19917000A Withdrawn DE19917000A1 (en) | 1999-04-15 | 1999-04-15 | Primary lithium ion cell, especially button cell, has positive electrode active material comprising PTFE |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE19917000A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080280191A1 (en) * | 2007-05-09 | 2008-11-13 | Rachid Yazami | Lithium fluoropolymer and fluoro-organic batteries |
-
1999
- 1999-04-15 DE DE19917000A patent/DE19917000A1/en not_active Withdrawn
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080280191A1 (en) * | 2007-05-09 | 2008-11-13 | Rachid Yazami | Lithium fluoropolymer and fluoro-organic batteries |
| WO2008141200A1 (en) | 2007-05-09 | 2008-11-20 | California Institute Of Technology | Lithium fluoropolymer and fluoro-organic batteries |
| EP2167228A4 (en) * | 2007-05-09 | 2011-11-30 | California Inst Of Techn | LITHIUM FLUOROPOLYMER AND FLUORO-ORGANIC BATTERIES |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| 8127 | New person/name/address of the applicant |
Owner name: MICROBATTERIE GMBH, 30419 HANNOVER, DE |
|
| 8127 | New person/name/address of the applicant |
Owner name: VARTA MICROBATTERY GMBH, 30419 HANNOVER, DE |
|
| 8139 | Disposal/non-payment of the annual fee |