FR2482371A1 - Battery cell contg. lithium negative electrode - using as positive active material soln. of Lewis acid and neutralising cpd. - Google Patents
Battery cell contg. lithium negative electrode - using as positive active material soln. of Lewis acid and neutralising cpd. Download PDFInfo
- Publication number
- FR2482371A1 FR2482371A1 FR8010168A FR8010168A FR2482371A1 FR 2482371 A1 FR2482371 A1 FR 2482371A1 FR 8010168 A FR8010168 A FR 8010168A FR 8010168 A FR8010168 A FR 8010168A FR 2482371 A1 FR2482371 A1 FR 2482371A1
- Authority
- FR
- France
- Prior art keywords
- lewis acid
- cpd
- ionic
- lithium
- salt
- 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
- 239000002841 Lewis acid Substances 0.000 title claims abstract description 17
- 150000007517 lewis acids Chemical class 0.000 title claims abstract description 17
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims description 14
- 229910052744 lithium Inorganic materials 0.000 title claims description 13
- 230000003472 neutralizing effect Effects 0.000 title 1
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims abstract description 14
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims abstract description 14
- 150000003839 salts Chemical class 0.000 claims abstract description 11
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims abstract description 9
- VMPVEPPRYRXYNP-UHFFFAOYSA-I antimony(5+);pentachloride Chemical compound Cl[Sb](Cl)(Cl)(Cl)Cl VMPVEPPRYRXYNP-UHFFFAOYSA-I 0.000 claims abstract description 9
- UHZYTMXLRWXGPK-UHFFFAOYSA-N phosphorus pentachloride Chemical compound ClP(Cl)(Cl)(Cl)Cl UHZYTMXLRWXGPK-UHFFFAOYSA-N 0.000 claims abstract description 8
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000002904 solvent Substances 0.000 claims abstract description 7
- 150000008040 ionic compounds Chemical class 0.000 claims description 7
- 239000000292 calcium oxide Substances 0.000 claims description 6
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 5
- 229910001947 lithium oxide Inorganic materials 0.000 claims description 5
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 claims description 4
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 4
- 239000005049 silicon tetrachloride Substances 0.000 claims description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 claims 1
- 229910003910 SiCl4 Inorganic materials 0.000 abstract description 4
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Inorganic materials [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 abstract description 4
- FDNAPBUWERUEDA-UHFFFAOYSA-N silicon tetrachloride Chemical compound Cl[Si](Cl)(Cl)Cl FDNAPBUWERUEDA-UHFFFAOYSA-N 0.000 abstract description 4
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 abstract description 3
- 229910001216 Li2S Inorganic materials 0.000 abstract 1
- 239000003792 electrolyte Substances 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- HBZVNWNSRNTWPS-UHFFFAOYSA-N 6-amino-4-hydroxynaphthalene-2-sulfonic acid Chemical compound C1=C(S(O)(=O)=O)C=C(O)C2=CC(N)=CC=C21 HBZVNWNSRNTWPS-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910013470 LiC1 Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- SOZVEOGRIFZGRO-UHFFFAOYSA-N [Li].ClS(Cl)=O Chemical compound [Li].ClS(Cl)=O SOZVEOGRIFZGRO-UHFFFAOYSA-N 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- JGIATAMCQXIDNZ-UHFFFAOYSA-N calcium sulfide Chemical compound [Ca]=S JGIATAMCQXIDNZ-UHFFFAOYSA-N 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- -1 salt anion Chemical class 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon 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
- H01M6/14—Cells with non-aqueous electrolyte
Landscapes
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Primary Cells (AREA)
Abstract
Description
Pile au lithium - chlorure de thionyle perfectionnée
La présente invention a pour objet une pile dont l'électrode négative comporte du lithium et dont ltélectrolyte comprend du chlorure de thionyle.Advanced lithium-thionyl chloride battery
The present invention relates to a battery whose negative electrode comprises lithium and whose electrolyte comprises thionyl chloride.
On connaît des piles dont l'électrode négative est confectionnée en lithium et dont la masse active positive jouant d'ailleurs également le rôle d'électrolyte comprend un solvant tel que le chlorure de thionyle et un soluté binaire constitué par l'association d'un acide de Lewis et d'un composé ionique ou sel, notamment le trichlorure d'aluminium et le chlorure de lithium. Le collecteur de courant positif est généralement constitué par un feutre de graphite noyé dans cette masse active. Batteries are known whose negative electrode is made of lithium and whose positive active mass also playing the role of electrolyte also comprises a solvent such as thionyl chloride and a binary solute constituted by the association of a Lewis acid and an ionic compound or salt, especially aluminum trichloride and lithium chloride. The positive current collector is generally constituted by a graphite felt embedded in this active mass.
Cependant, on constate que dans de telles piles il se produit en début de décharge une baisse notable de la tension #qui remonte ensuite pour se stabiliser à une valeur sensiblement constante dans le temps, dite tension de palier ou tension stationnaire. Si une telle baisse d'ailleurs dénommée "puits de tension" ne présente pas d'inconvénients majeurs dans certaines applications il n'en est pas de même dans le cas où l'on exige de la pile la totalite de sa tension dès le début- de la décharge. La Demanderesse a donc cherché d'une part à éliminer ledit puits de tension et d'autre part à augmenter la valeur de la tension stationnaire de la pile. However, it is found that in such batteries there occurs at the start of discharge a noticeable drop in the voltage # which then rises to stabilize at a value substantially constant over time, called the bearing voltage or stationary voltage. If such a drop, moreover, called "voltage sink" does not present major drawbacks in certain applications, it is not the same in the case where the battery is required to have all of its voltage from the start. - of the discharge. The Applicant has therefore sought on the one hand to eliminate said voltage sink and on the other hand to increase the value of the stationary voltage of the cell.
L'invention a donc pour objet une pile comprenant une électrode négative de lithium, une matière active positive comportant un solyant notamment du chlorure de thionyle et un soluté binaire composé d'un acide de Lewis et d'un composé ionique ou sel, caractérisée par le fait que ledit acide de Lewis est choisi dans le groupe constitué par le pentachlorure d'antimoine, le pentachlorure de-phosphore et le tétrachlorure de silicium. The subject of the invention is therefore a battery comprising a negative lithium electrode, a positive active material comprising a solurant, in particular thionyl chloride, and a binary solute composed of a Lewis acid and an ionic compound or salt, characterized by the fact that said Lewis acid is selected from the group consisting of antimony pentachloride, phosphorus pentachloride and silicon tetrachloride.
Selon un mode de réalisation, ledit acide de Lewis--est le penta- chlorure d'antimoine ledit composé ionique ou sel-étant l'oxyde de lithium ou l'oxyde de calcium. According to one embodiment, said Lewis acid - is antimony pentachloride, said ionic compound or salt - being lithium oxide or calcium oxide.
Selon un autre mode de réalisation ledit acide de Lewis est le pentachlorure de phosphore ou le-tétrachlorure de silicium, ledit composé ionique ou sel étant le chlorure, le sulfure, l'oxyde ou le fluorure de lithium ou encore l'oxyde ou le sulfure de calcium. According to another embodiment, said Lewis acid is phosphorus pentachloride or silicon tetrachloride, said ionic compound or salt being chloride, sulfide, lithium oxide or fluoride or also oxide or sulfide calcium.
D'autres caractéristiques et avantages de l'invention ressortent de la description qui suit donnée à titre d'exemple purement illustratif mais nullement limitatif en référence aux diagrammes annexés dans lesquels
La figure 1 représente la partie initiale de la courbe de décharge d'une pile au lithium selon la technique antérieure.Other characteristics and advantages of the invention will emerge from the description which follows, given by way of purely illustrative but in no way limiting, with reference to the attached diagrams in which
FIG. 1 represents the initial part of the discharge curve of a lithium battery according to the prior art.
La figure 2 représente la partie initiale des-eourbes de décharge de piles au lithium selon l'invention. FIG. 2 shows the initial part of the lithium battery discharge tubes according to the invention.
On a monté des piles,,,1'essai constituées par une électrode négative au lithium avec collecteur en nickel et une électrode positive inerte en feutre de graphite. L'électrolyte baigne le lithium sur une face et imprégne 11 électrode positive ; il est constitué de chlorure de thionyle en tant que solvant et d'un soluté binaire. Ces piles 2 ont été déchargées à une densité de courant de 6,#mA/cm -apres conser- vation pendant 15 jours à 250C ou 7 jours à 700C. Batteries were mounted, the test consisting of a negative lithium electrode with nickel collector and an inert positive electrode made of graphite felt. The electrolyte bathes the lithium on one side and impregnates 11 positive electrode; it consists of thionyl chloride as a solvent and a binary solute. These batteries 2 were discharged at a current density of 6, # mA / cm - after storage for 15 days at 250C or 7 days at 700C.
La figure. 1 représente la tension E en volts en fonction du temps t en secondes pour une pile au lithium dont l'électrolyte qui est en meme temps la matière active positive comporte du chlorure de thionyle SOC12 comme solvant, et le soluté binaire du trichlorure d' aluminium Aloi3 et du chlorure de lithium LiC1, comme précédemment mentionné. The figure. 1 represents the voltage E in volts as a function of time t in seconds for a lithium battery whose electrolyte which is at the same time the positive active material comprises thionyl chloride SOC12 as solvent, and the binary solute of aluminum trichloride Aloi3 and lithium chloride LiC1, as previously mentioned.
On voit que la tension qui présente une valeur initiale de 3,5 volts diminue pour atteindre à l'issue de 5 secondes de décharge une valeur de 0,9 voltS. Elle se stabilise ensuite à une valeur de 2,9 volts. We see that the voltage which has an initial value of 3.5 volts decreases to reach after 5 seconds of discharge a value of 0.9 voltS. It then stabilizes at a value of 2.9 volts.
La figure 2 représente les mêmes paramètres que ci-dessus mais pour des piles selon l'invention. FIG. 2 represents the same parameters as above but for batteries according to the invention.
Plus précisément, la courbe A correspond à une pile dont le soluté d'électrolyte comprend du pentachlorure d'antimoine SbCl5 et du chlorure de lithium Licol. On voit que le puits de potentiel existe toujours mais il est cependant moins- prononcé que pour une pile classique Mais de plus, la tension de palier est plus élevée soit 3,5 volts au lieu de 2,9. More precisely, curve A corresponds to a cell in which the electrolyte solute comprises antimony pentachloride SbCl5 and lithium chloride Licol. We see that the potential well still exists but it is however less pronounced than for a conventional battery. But moreover, the bearing voltage is higher at 3.5 volts instead of 2.9.
La courbe B correspond à une pile dont le soluté d'électrolyte comprend SoC1 et de l'oxyde de lithium Li20 ou de l'oxyde de calcium CaO. Curve B corresponds to a battery in which the electrolyte solute comprises SoC1 and lithium oxide Li20 or calcium oxide CaO.
On constate que le puits de potentiel n'-existe~plus et qu'en outre la tension de palier est élevée soit 3,6 volts. It can be seen that the potential well does not exist anymore and that, in addition, the bearing voltage is high, ie 3.6 volts.
Les autres courbes représentent les caractéristiques de décharge de piles dont le soluté comprend du pentachlorure de phosphore PCl5 (courbes C.D.E.F.), ou du tétrachiorure de siliciun SiC14 (courbes
G.H.I.J.), le deuxième composant étant soit le chlorure de lithium (courbes C et G), soit le sulfure de lithium ou de calcium (courbes D et H) soit l'oxyde de lithium et de calcium (courbes E et I) soit le fluorure de lithium (courbes F et J).The other curves represent the discharge characteristics of cells, the solute of which comprises phosphorus pentachloride PCl5 (curves CDEF), or silicon tetrachioride SiC14 (curves
GHIJ), the second component being either lithium chloride (curves C and G), or lithium or calcium sulfide (curves D and H) or lithium and calcium oxide (curves E and I) or lithium fluoride (curves F and J).
On voit que les courbes de décharge sont sensiblement horizontales, la tension de palier étant de l'ordre de 2,9 à 3,1 volts dans le cas de PCL. et de l'ordre de 3,22 à 3,55 volts dans le cas de SiCl4. We see that the discharge curves are substantially horizontal, the bearing voltage being of the order of 2.9 to 3.1 volts in the case of PCL. and of the order of 3.22 to 3.55 volts in the case of SiCl4.
5
En ce qui concerne maintenant la concentration des composants du soluté binaire, celle-ci est comprise entre 0,2-5 mole/litre de solvant et la concentration de saturation.5
As regards now the concentration of the components of the binary solute, this is between 0.2-5 mole / liter of solvent and the saturation concentration.
Le soluté binaire est constitué par l'acide de Lewis complètement neutralisé au sens de la chloro-acido-basicité, par le composé ionique ou sel. The binary solute is constituted by Lewis acid completely neutralized in the sense of chloro-acid-basicity, by the ionic compound or salt.
Pour fixer les idées, le rapport molaire sel doit être égal
Y acide à Y dans lequel X est la valence de l'anion du sel soit 1 pour LiCl,
X 2 pour Li2O, et Y le pouvoir "accepteur" de l'acide de Lewis soit 1 pour lC137 SbCl5, pCl5 et 2 pour SiCl4.To fix ideas, the salt molar ratio must be equal
Y acid to Y in which X is the valence of the salt anion or 1 for LiCl,
X 2 for Li2O, and Y the "acceptor" power of Lewis acid, ie 1 for IC137 SbCl5, pCl5 and 2 for SiCl4.
On voit que les piles selon l'invention présentent vis-à-vis des piles au lithium connues une grande stabilité de décharge associée à des performances améliorées. It can be seen that the batteries according to the invention have, with respect to known lithium batteries, high discharge stability associated with improved performance.
Elles trouvent des applications avantageuses dans tous les domaines d'utilisation des piles au lithium. They find advantageous applications in all fields of use of lithium batteries.
Bien entendu 1' invention n'est nullement limitée aux modes de réalisation décrits mais elle en coutre au contraire toutes les variantes. Of course, the invention is in no way limited to the embodiments described, but on the contrary it covers all the variants thereof.
Claims (4)
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR8010168A FR2482371B1 (en) | 1980-05-07 | 1980-05-07 | LITHIUM BATTERY - PERFECTED THIONYL CHLORIDE |
| FR8100209A FR2497607B2 (en) | 1980-05-07 | 1981-01-08 | IMPROVED THIONYL LITHIUM CHLORIDE BATTERY |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR8010168A FR2482371B1 (en) | 1980-05-07 | 1980-05-07 | LITHIUM BATTERY - PERFECTED THIONYL CHLORIDE |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| FR2482371A1 true FR2482371A1 (en) | 1981-11-13 |
| FR2482371B1 FR2482371B1 (en) | 1985-10-25 |
Family
ID=9241712
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| FR8010168A Expired FR2482371B1 (en) | 1980-05-07 | 1980-05-07 | LITHIUM BATTERY - PERFECTED THIONYL CHLORIDE |
Country Status (1)
| Country | Link |
|---|---|
| FR (1) | FR2482371B1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0062647A4 (en) * | 1980-10-17 | 1983-02-09 | Gte Laboratories Inc | Electrochemical cell. |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3926669A (en) * | 1972-11-13 | 1975-12-16 | Gte Laboratories Inc | Electrochemical cells having an electrolytic solution comprising a covalent inorganic oxyhalide solvent |
| FR2341952A1 (en) * | 1976-02-18 | 1977-09-16 | Union Carbide Corp | ELECTRIC BATTERY WITH DIVIDED AND ELASTICALLY PUSHED BACK CATHODE |
| US4093784A (en) * | 1977-08-26 | 1978-06-06 | The United States Of America As Represented By The Secretary Of The Army | Lithium primary cell |
| GB2013390A (en) * | 1978-01-31 | 1979-08-08 | Accumulateurs Fixes | Lithium primary cell containing thionyl chloride |
| US4184007A (en) * | 1978-12-15 | 1980-01-15 | Union Carbide Corporation | Nonaqueous battery construction |
-
1980
- 1980-05-07 FR FR8010168A patent/FR2482371B1/en not_active Expired
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3926669A (en) * | 1972-11-13 | 1975-12-16 | Gte Laboratories Inc | Electrochemical cells having an electrolytic solution comprising a covalent inorganic oxyhalide solvent |
| FR2341952A1 (en) * | 1976-02-18 | 1977-09-16 | Union Carbide Corp | ELECTRIC BATTERY WITH DIVIDED AND ELASTICALLY PUSHED BACK CATHODE |
| US4093784A (en) * | 1977-08-26 | 1978-06-06 | The United States Of America As Represented By The Secretary Of The Army | Lithium primary cell |
| GB2013390A (en) * | 1978-01-31 | 1979-08-08 | Accumulateurs Fixes | Lithium primary cell containing thionyl chloride |
| US4184007A (en) * | 1978-12-15 | 1980-01-15 | Union Carbide Corporation | Nonaqueous battery construction |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0062647A4 (en) * | 1980-10-17 | 1983-02-09 | Gte Laboratories Inc | Electrochemical cell. |
Also Published As
| Publication number | Publication date |
|---|---|
| FR2482371B1 (en) | 1985-10-25 |
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