AU731463B2 - Method and anode for improving the power density of lithium secondary batteries - Google Patents
Method and anode for improving the power density of lithium secondary batteries Download PDFInfo
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- AU731463B2 AU731463B2 AU57484/98A AU5748498A AU731463B2 AU 731463 B2 AU731463 B2 AU 731463B2 AU 57484/98 A AU57484/98 A AU 57484/98A AU 5748498 A AU5748498 A AU 5748498A AU 731463 B2 AU731463 B2 AU 731463B2
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- Prior art keywords
- anode
- boric acid
- additives
- lithium
- iii
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims description 18
- 229910052744 lithium Inorganic materials 0.000 title claims description 18
- 238000000034 method Methods 0.000 title claims description 10
- 239000000654 additive Substances 0.000 claims description 19
- 239000004327 boric acid Substances 0.000 claims description 9
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical class OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 8
- -1 boric acid ester Chemical class 0.000 claims description 8
- 229920000642 polymer Polymers 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 5
- 229910052723 transition metal Inorganic materials 0.000 claims description 5
- 150000003624 transition metals Chemical class 0.000 claims description 5
- 150000002642 lithium compounds Chemical class 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 125000001931 aliphatic group Chemical group 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 claims description 3
- 239000007784 solid electrolyte Substances 0.000 claims 2
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 150000001450 anions Chemical class 0.000 description 17
- 239000003792 electrolyte Substances 0.000 description 11
- 229910001416 lithium ion Inorganic materials 0.000 description 11
- 150000003839 salts Chemical class 0.000 description 9
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 7
- 238000009795 derivation Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 230000000996 additive effect Effects 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 4
- 208000020960 lithium transport Diseases 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000013543 active substance Substances 0.000 description 3
- 239000010405 anode material Substances 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
- 239000010406 cathode material Substances 0.000 description 3
- 230000003247 decreasing effect Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 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
- 239000004809 Teflon Substances 0.000 description 2
- 229920006362 Teflon® Polymers 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical compound FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 229910052768 actinide Inorganic materials 0.000 description 1
- 150000001255 actinides Chemical class 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229920005596 polymer binder Polymers 0.000 description 1
- 239000002491 polymer binding agent Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000012360 testing method Methods 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
- 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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/02—Boron compounds
- C07F5/04—Esters of boric acids
-
- 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
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative 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
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
-
- 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
- H01M6/162—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte
- H01M6/168—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte by additives
-
- 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
- H01M6/18—Cells with non-aqueous electrolyte with solid electrolyte
- H01M6/181—Cells with non-aqueous electrolyte with solid electrolyte with polymeric electrolytes
-
- 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
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Description
Method and Anode for Improving the Power Density of Lithium Secondary Batteries The invention relates to a method and anode for improving the power density of lithium secondary batteries, especially those containing solid polymer solutions.
In cell arrangements, or other arrangements, an improved materials utilization factor is needed in order to be able to meet the market demands. If charge transport from anode material to cathode material in a secondary battery is effected preferably by an electrolyte, or an electrolyte solution respectively, this can be put down to the fact that any material will be transported by an existing potential, and as a consequence, also positively charged ions will be transported by electrolytes to the negatively charged electrode, which applies to anions vice versa.
The electrolyte's current density is expressed as follows: I LE Aiti j i) (1) in which LE means the conductivity of the electrolyte solution, A0 means the potential difference between anode and cathode materials, tir means the reduced transport index for transport species and Agi means the difference in chemical potential of species between anode and cathode materials.
Since all materials in the anode are diluted per definition, Ali will be close to zero, and for usual batteries as explained by way of illustration this will lead to an equivalent of the 1st Ohm's Law.
**There may be voltage values higher than allowed for the system. This may lead to risks or damages that should be avoided by way of prevention.
Finally, polymer bonds are considered to be disadvantageous, and anions are not immobilised. The lithium's transport capacity is insufficient.
One aim of the present invention is to provide an additive, which will improve the power density and, at the same time, secure operational reliability, in particular 2 when implemented in lithium secondary batteries. Advantageously, a preferred form of the invention should also achieve a positive deviation of the 1 st Ohm's Law, reduce the salt exhaustion, and increase the number of cycles, or the cycle strength, when implemented in a lithium secondary battery.
It would also be desirable to provide process steps in the manufacture of batteries whereby the improvements described above can be implemented in practice.
Accordingly, in a first aspect of the invention, there is provided a method for improving the power density of lithium secondary batteries, characterized in that boric acid esters and/or boric acid ester derivates, or compounds thereof, are employed as additives at the anode in the manufacture of lithium batteries.
Said additive will bring about a reduction of the so-called salt exhaustion, a high lithium transport capacity, and a positive derivation of the 1 st Ohm's Law. This also will lead to an increased cycle strength of the battery system as well as an improved power density for the potentials specified. Compare the attached figures 3 and 4 in particular, which show the advantages of a cell system in accordance with the invention.
Preferably, boric esters and/or boric ester derivates are used as lithium complex compounds such as H H O 0 l /P B Li+
R
2 0- C- R 2
H
I
I
L
i and/or R/R Li+ and/or Hm MB M Li+ where the partial groups R, and R 2 can be aromatic and/or aliphatic, and in formula Ill.- "M" is a transition metal, and the cyclopentadienyl groups may contain Fluor instead of H.; SO- .Per definition, transition metals are elements the atoms of which have incomplete d shells, or may form one or more cations with such incomplete d shells. Therefore, and according to the IUPAC recommended notation, transition metals include in-the 4' period the elements from oleo Sc through to Zn, having atomic numbers from 21 through to 30, in the 50' period the elements from Y through to Cd, having atomic numbers from 39 through to 48, in the 6 period the elements from La through to Hg, together with the lanthanoid series which have the .e 4f shell filled up, having atomic numbers from 57 through to 80, and finally in the 7 period the actinoid series through to Lr, having atomic numbers from 89 through to 103.
Preferably, boric acid esters will be employed.
The partial groups will cause electrochemical stability and solubility in organic solvents. Due to the large and voluminous partial groups the negative charge is distributed, and therefore, it is very unlikely to happen that Li* may form ion pairs or complex species, and the organic solvent contains the salt in dissolved or dissociated form.
The additives are added preferably on the anode side.
The additives are added in quantities from 0 to 20 per cent (by weight), preferably 5 to per cent (by weight).
The anode according to the invention, especially those as employed in lithium secondary batteries and those containing solid polymer solutions, contains in its immediate vicinity additives of boric acid and/or boric acid ester derivates, or compounds thereof.
This will cause a comparably high current to flow with a potential set low, and in particular bring about effects as a stable system and higher number of cycles, or increased cycle strength, respectively.
The anode consists of a substance that is able to intercalate lithium ions and/or lithium and conducting salts dissolved in solvents and/or in a polymer binder and/or a conducting carbon black and/or the additive.
o **o *i o* o* *o Especially suitable are those anodes which contain as an additive lithium compounds of boric acid esters and/or boric acid ester derivates in form of complexes such as 0
B
-'N
H
I.
O--C-R,
I
-M
O-C RI
H,
Li
R
2 -C--0
I
and/or
RI
Li+ a a a a it and/or Co 0
H
Under consideration of expediency, such additives should be contained in the anodes in quantities over 0 up to 20 per cent by weight, preferably from 5 up to 15 per cent by weight.
The following is a more detailed explanation of the invention, with references to the attached drawings. The drawing show the following:- Figure I a schematic cross section of a battery, for example a lithium ion battery LiC/PEO, lithium salt ILi Mn 2 O, without salt exhaustion, with extremely low electric current flows in a very short period of time (ideal case) Figure 2 a schematic cross section of the same system, but in contrast to figure 1 the curves show the behaviour when bigger current flows are used Figure 3 ****again a schematic cross section of the same system, the graphs here, however, show the behaviour under small and big current flow conditions, without salt exhaustion to happen Figure 4 trends shown as curves for smaller, medium and bigger current flow conditions Figure curves as shown in figure 4, but as ideal case, with immobilised anions Figure 6 schematic illustrative curves on how cycle strength can be increased in case of using polyethylenoxid (PEO) Figure 7 Curves to illustrate the positive derivation of the 1st Ohm's Law when additives are used, compared with graphs having no positive derivation Figure 8 a schematic illustration on anodes electrolyte cathodes in case of additives used not used Figure 9 current voltage diagram to illustrate the results from the examples used In arrangements as schematically illustrated in figure 1, there will be no salt exhaustion in case of extremely low current flows in short time cycles. This applies in particular to the lithium ion batteries, outlined as sketch infigure 1, where under ideal conditions the anions are not immobilised. For that reason, only small current flows can be drawn without gradient.
Figure 2 illustrates these condition in case of bigger current flows for the same system on the basis of a lithium ion battery, where local salt exhaustion will occur. As the lithiium ions move under the influence of a mass equilibrium the concentration thereof is constant, by approximation The anions move towards the electrolyte at the positive electrode. As there is no anions dispensed by the electrodes a concentration gradient will build up. According to Kohlrausch's Law, the ion conductivity depends on the electrolyte concentration the lower the concentration, the lower the conductivity. Furthermore, a conductivity gradient builds up as a concentration gradient develops, and local electrolyte resistance increases with decreasing electrolyte conductivity. As a consequence, the increase in the local electrolyte resistance entails a potential drop As shown in figure 3, the anions are now immobilised within the polymer matrix of the elec- S* trolyte, according to the invention.
O*l* In this way, both big and small current flows can be used without having any problems with *salt exhaustion effects and following potential drops, as also shown in figure 5 as trend of graphs in an ideal case with immobilised anions.
o*oo As far as medium and bigger current flows are concerned, the referenced trends are summarised in the graphs shown in figure 4.
The ideal case with immobilised anions as illustrated in figure 5 shall be taken as an example to give a more detailed explanation below.
The anions are not mechanically immobilised but their transport capacity is very small compared with the lithium's one.
In case the anions are mechanically immobilised, the complex constant is very high, and thd lithium transport capacity drops. Also, the overall conductivity drops as the complex constant between anions and lithium is high.
In case the anions are chemically immobilised, the complex constant between Li* and anion is very high, in contrast to the overall conductivity which is very low. If, however, the anion transport is very small compared with the Li* transport capacity, then there will be no significant complexes between anions and cations, which will lead to a high conductivity value.
Figure 6 is based on the fact that if a bigger current flow is needed a higher potential must be used. High potentials result in an only small number of cycles, or a rather qualified cycle strength. This is shown in figure 6, taking PEO solvent as an example.
In addition, it can be seen from figure 6 that according to the invention current levels can be kept constant with decreased potentials, the sizes of which are so that the PEO solvent is stable. Using substances according to the invention, the cycle capability could be improved by decreasing potentials and current flows kept on a constant level. The reduced potential **brings about a higher number of cycles, or a better cycle strength, respectively. Based on a lithium ion battery system, as used as illustrative example in figure 1, it could be shown that, S according to the invention, after adding substances, as detailed in the patent claims, to the electrolyte binder material in the anode the potential could be reduced without reducing current flow density, as drawn as an example in figure 6, which is considered a special advantage of the present invention.
ao..
,o In test series, the power density could be increased, and corresponding proof established. In this context, figure 7 is a schematic diagram of the so-called positive derivations of the 1' Ohm's Law together with graphs showing the normal course of the 1 Ohm's Law for ordinary batteries in lithium ion battery systems as described.
For the investigation, the potential had been fixed to a constant level. Then, the additive complexes, resp. the substances found, were added and a positive derivation of the 1 s Ohm's Law determined. This means that a higher current flow is achieved compared with that one achievable under normal graph courses according to the 1' Ohm's Law. Thus, the power density of the system is improved.
From the equation in figure 8 as well as from the sketch, it can be seen that the transport capacity of the anions comes close to zero. the chemical potential difference has no impact at all on the current flow density.
If a lithium compound of a boric acid ester derivate is added, the partial excess energy of lithium ions becomes permanently positive. This fact is based on an increase in the current flow density as well as an increase in the lithium transport capacity; i.e., 8t' 8 x 0 and RT (S In x u 8x) 0 and tr' e Ap 0 Volt (2) This will lead to a positive derivation of the 1' Ohm's Law.
"For predetermined cell designs and potentials, a bigger current may be drawn into an outer circuit, if the system shows a positive deviation from the 1" Ohm's Law, this is equivalent to an increase in power density.
Example 1 (comparative example) Formulation without Lithium-bis[1, 2 -benzenediolato(2-)-O,O'Iborate(1-)(LiBSE) Active substance content in (by weight) :Graphite (KS6 type) 90.29 Conducting carbon black (super P type) 4.74 F6 TEFLON binder 4.97 lectrode gross weight: 13.9 mg; weight of active KS6: 12.55 mg (equivalent to 4.67 mAh) t0 Example 2 Formulation with Lithium-bis[1,2-benzenediolato(2-)-O,O']borate(1-)(LiBSE) Active substance (by weight) Graphite (KS6 type) 82.08 Conducting carbon black (super P type) 4.30 TEFLON binder 4.53 LiBSE 9.09 Electrode gross weight: 11.3 mg; weight of active KS6: 9.3 mg (equivalent to 3.46 mAh) For both examples, measurements were made in a lithium half cell, with an active surface of approx. 1 cm 2 (standard electrolyte LP 30: EC DMC 1 m LiPF 6 chart speed: 0.1 mV/s).
For preparing the electrodes, corresponding active substances were mixed together in a mortar, and pressed onto the nickel mesh.
For both the formulations, a cyclovoltamogram was taken using a triggerable potentiostate, as shown in figure 9 (voltage-current diagram). In addition, figure 9 leads to the conclusion that both cathode and anode current is increased, which means that the LiBSE system ca- ,pacity (example 2) is increased, compared to the system w/o LiBSE (example 1).
6 6 o* C o 6 0
Claims (10)
1. Method for improving the power density of lithium secondary batteries, characterized in that boric acid esters and/or boric acid ester derivates, or compounds thereof, are employed as additives at the anode in the manufacture of lithium batteries.
2. Method according to claim 1, characterized in that it is performed in the manufacture of lithium secondary batteries containing solid electrolyte polymer solutions.
3. Method according to claim 1 or 2, characterized in that the boric acid esters and/or boric acid ester derivates are present in the form of lithium compounds having a formula selected from the group consisting of I, II, III or combinations thereof, wherein H H I I R-C-O O-C-R 1 I is B Li+ R2-C-O O-C-R 2 I I H H II is R B RI Li *0 *O O* *o• and III is M B M Li H H and wherein the partial groups R 1 and R 2 can be aromatic and/or aliphatic, and in formula III M is a transition metal, and the cyclopentadienyl groups may contain Fluor instead of H.
4. Method according to claim 3, characterized in that the additives are added in quantities from 0 to 20 per cent by weight relative to the anode.
Method according to claim 4, characterized in that the additives are added in a quantity of 5 to 15 per cent by weight relative to the anode.
6. Anode for lithium polymer batteries, characterized in that boric acid esters and/or boric acid ester derivates, or the compounds thereof, are contained as additives in the anode.
7. Anode according to claim 6, characterized in that the additives are lithium compounds of boric acid esters and/or boric acid ester derivates having a formula o selected from the group consisting of I, II, III or combinations thereof, wherein D o* H H I I** R-C -O O-C-R I is B Li+ R 2 -C-O O-C-R 2 I I H H ooooo: 13 IIis R RB Li O O H HH and III is M B M Li CO OC-( H- H and wherein the partial groups R 1 and R 2 can be aromatic and/or aliphatic, and in formula III M is a transition metal, and the cyclopentadienyl groups may contain Fluor instead of H.
8. Anode according to claim 6 or 7, characterized in that the additives are contained in quantities from 0 to 20 per cent by weight relative to the anode.
9. Anode according to claim 8, characterized in that the additives are S contained in quantities from 5 to 15 per cent by weight relative to the anode.
10. Lithium secondary battery containing solid electrolyte polymer solutions and incorporating an anode according to any one of claims 6 to 9. *o 14 DATED this 8th day of January 2001 DILO TRADING AG WATERMARK PATENT TRADEMARK ATTORNEYS UNIT 1 THE VILLAGE RIVERSIDE CORPORATE PARK NORTH RYDE NSW 2113 AUSTRALIA P1 031 6AUOO
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19654057 | 1996-12-23 | ||
DE19654057A DE19654057C2 (en) | 1996-12-23 | 1996-12-23 | Process for improving the power density of lithium secondary batteries |
PCT/DE1997/002974 WO1998028807A1 (en) | 1996-12-23 | 1997-12-19 | Method and anode for improving the power density of lithium secondary batteries |
Publications (2)
Publication Number | Publication Date |
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AU5748498A AU5748498A (en) | 1998-07-17 |
AU731463B2 true AU731463B2 (en) | 2001-03-29 |
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AU57484/98A Ceased AU731463B2 (en) | 1996-12-23 | 1997-12-19 | Method and anode for improving the power density of lithium secondary batteries |
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EP (1) | EP0948826A1 (en) |
JP (1) | JP2001506799A (en) |
KR (1) | KR20000062304A (en) |
AU (1) | AU731463B2 (en) |
BR (1) | BR9714165A (en) |
CA (1) | CA2275969A1 (en) |
DE (1) | DE19654057C2 (en) |
IL (1) | IL130566A0 (en) |
RU (1) | RU2175798C2 (en) |
WO (1) | WO1998028807A1 (en) |
Families Citing this family (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6150053A (en) * | 1997-06-06 | 2000-11-21 | Matsushita Electric Industrial Co., Ltd. | Non-aqueous electrolyte secondary battery |
DE19910968A1 (en) * | 1999-03-12 | 2000-11-09 | Merck Patent Gmbh | Use of additives in electrolytes for electrochemical cells |
KR100553736B1 (en) * | 1999-09-02 | 2006-02-20 | 삼성에스디아이 주식회사 | Composition of active material for lithium secondary batteries |
JP2004511879A (en) | 2000-06-16 | 2004-04-15 | アリゾナ ボード オブ リージェンツ, ア ボディ コーポレイト アクティング オン ビハーフ オブ アリゾナ ステート ユニバーシティ | Conductive polymer composition for lithium battery |
US7527899B2 (en) | 2000-06-16 | 2009-05-05 | Arizona Board Of Regents For And On Behalf Of Arizona State University | Electrolytic orthoborate salts for lithium batteries |
KR20020023145A (en) | 2000-09-21 | 2002-03-28 | 가나이 쓰도무 | Organic borate lithium compounds and nonaqueous electrolytes using the same |
JP5666225B2 (en) * | 2010-09-16 | 2015-02-12 | 株式会社豊田中央研究所 | Negative electrode for lithium ion secondary battery and lithium ion secondary battery |
CN102964369B (en) * | 2012-10-24 | 2016-04-06 | 中国科学院青岛生物能源与过程研究所 | One class in polymer type boric acid ester lithium salts and its preparation method and application |
CN104183867B (en) * | 2014-08-12 | 2018-06-19 | 中国科学院青岛生物能源与过程研究所 | A kind of single ion conductor nano-particle reinforcement lithium battery diaphragm or method for preparing polymer electrolytes and application |
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US4195120A (en) * | 1978-11-03 | 1980-03-25 | P. R. Mallory & Co. Inc. | Hydrogen evolution inhibitors for cells having zinc anodes |
JPH0448709A (en) * | 1990-06-15 | 1992-02-18 | Japan Carlit Co Ltd:The | Manufacture of solid electrolytic capacitor |
EP0682817A1 (en) * | 1993-02-12 | 1995-11-22 | Valence Technology, Inc. | Electrodes for rechargeable lithium batteries |
DE4316104A1 (en) * | 1993-05-13 | 1994-11-17 | Manfred Wuehr | Electrolyte for use in a galvanic cell |
EP0631340B1 (en) * | 1993-06-18 | 2001-11-21 | Hitachi Maxell Ltd. | Organic electrolytic solution cell |
JP3208243B2 (en) * | 1993-11-18 | 2001-09-10 | 三洋電機株式会社 | Non-aqueous battery |
US5597663A (en) * | 1995-05-30 | 1997-01-28 | Motorola, Inc. | Low temperature molten lithium salt electrolytes for electrochemical cells |
DE19633027A1 (en) * | 1996-08-16 | 1998-02-19 | Merck Patent Gmbh | Process for the production of new lithium borate complexes |
-
1996
- 1996-12-23 DE DE19654057A patent/DE19654057C2/en not_active Expired - Fee Related
-
1997
- 1997-12-19 RU RU99116263/09A patent/RU2175798C2/en active
- 1997-12-19 IL IL13056697A patent/IL130566A0/en unknown
- 1997-12-19 JP JP52822998A patent/JP2001506799A/en active Pending
- 1997-12-19 CA CA002275969A patent/CA2275969A1/en not_active Abandoned
- 1997-12-19 AU AU57484/98A patent/AU731463B2/en not_active Ceased
- 1997-12-19 KR KR1019997005724A patent/KR20000062304A/en not_active Application Discontinuation
- 1997-12-19 WO PCT/DE1997/002974 patent/WO1998028807A1/en not_active Application Discontinuation
- 1997-12-19 BR BR9714165-8A patent/BR9714165A/en unknown
- 1997-12-19 EP EP97953650A patent/EP0948826A1/en not_active Withdrawn
Non-Patent Citations (1)
Title |
---|
"A NEW CLASS OF ELECTROCHEM....SALTS FOR LITHIUM BATTERIES" "SYNTHESIS AND PROPERTIES OF SOME LITHIUM ORGANOBORATES" BARTLEL J. ET AL, J. ELECTRO. SOC.,VOL.143,#11,NOV 1996 * |
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AU5748498A (en) | 1998-07-17 |
KR20000062304A (en) | 2000-10-25 |
EP0948826A1 (en) | 1999-10-13 |
RU2175798C2 (en) | 2001-11-10 |
DE19654057C2 (en) | 2001-06-21 |
WO1998028807A1 (en) | 1998-07-02 |
DE19654057A1 (en) | 1998-06-25 |
CA2275969A1 (en) | 1998-07-02 |
JP2001506799A (en) | 2001-05-22 |
IL130566A0 (en) | 2000-06-01 |
BR9714165A (en) | 2002-01-02 |
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