GB2087858A - High surface area conductors - Google Patents
High surface area conductors Download PDFInfo
- Publication number
- GB2087858A GB2087858A GB8134943A GB8134943A GB2087858A GB 2087858 A GB2087858 A GB 2087858A GB 8134943 A GB8134943 A GB 8134943A GB 8134943 A GB8134943 A GB 8134943A GB 2087858 A GB2087858 A GB 2087858A
- Authority
- GB
- United Kingdom
- Prior art keywords
- limo2
- surface area
- high surface
- transition metal
- oxide
- 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
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Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G51/00—Compounds of cobalt
- C01G51/40—Cobaltates
- C01G51/42—Cobaltates containing alkali metals, e.g. LiCoO2
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/40—Nickelates
- C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/50—Solid solutions
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
-
- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
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- 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
Abstract
High surface area ion conductors LiMO2 (where M is a transition metal e.g. Fe, Co or Ni) which may be converted electrochemically to ion conductor LixMO2, where x is less than 1, may be prepared by precipitating a gelatinous form of an oxide of transition metal M from a solution containing ions of the transition metal, converting the gelatinous oxide to NaMO2 e.g. by heating with NaOH, and converting the NaMO2 to LiMO2 by ion exchange (e.g. by heating the NaMO2 in a melt of a soluble Li salt). LiMO2 and LixMO2 may be used as solid electrodes in electrochemical cells.
Description
SPECIFICATION
High surface area conductors
This invention is concerned with a method of preparing a high surface area form of ion conductors such as LiCoO .
European Patent Application No 80300876-2 (Publication No 0017400) relates to ion conductors having the formula AXMyO2 and having the layers of the a-NaCrO2 structure, in which formula A is Li, Na or K;
M is a transition metal; x is less than 1 and y is approximately equal to 1, the A+ cation vacancies in the ion conductor having been created by A+ cation extraction. Such ion conductors have potential application as solidsolution electrodes in electrochemical cells. An example of an ion conductor of the above formula is LixCoO2. This may be prepared according to the above application by firstly heating a mixture of Li2CO3 and CoCO2 in air at 900"C for 20 hours followed by two further and similar firings to give a product of approximate compostion LiCoO2.Li+ ions are then extracted electrochemically to give Li#Co02.
A method of preparing a product of approximate composition LiMO2 in a much higher surface area form than the product made by the above method, where M is a transition metal such as Co, has now been devised. A higher surface area product has been found to give certain advantages in applications in electrochemical cells.
Thus, the present invention provides a method of preparing a high surface area form of LiMO2, where M is a transition metal, which comprises the steps of
(i) precipitating a gelatinous form of an oxide of the transition metal M from a solution containing ions of the transition metal M;
(ii) converting the oxide prepared in step (i) to NaMO2, and
(iii) converting the NaMO2 to LiMO2 by ion exchange.
X-ray diffraction analysis has confirmed the higher surface area and hence smaller particle size of the product of the invention in the specific case of LiCoO2 than the product of the method described in European Patent Application No 80300876-2. This has resulted in the product of the invention having comparatively improved electrochemical characteristics as evidenced by measurements of the diffusion coefficient of the Li + ion in the compound and in derivatives thereof from which
Li+ ions have been extracted electrochemically, e.g. compounds of the formula LixCoO2 where x is less than 1. It should be noted that the formulae given in this specification may be approximate in the sense that precise stoichiometry may not be achieved in practice.
Step (i) of the present method is known in the art and must be carried out with some care in order to produce a gelatinous precipitate of the oxide, e.g. Co3O4, which may be precipitated from a Co(ll) ion containing solid tion. Examples of other oxides which may be precipitated in step (i) are y-Fe203 and Uni20 .
Step (ii) is preferably carried out by heating the oxide with a stoichiometric amount of
NaOH. It may be carried out at relatively low temperatures (e.g. approximately 150 C) ar d, when the transition metal is Co, surprisingly gives rise to NaCoO2 of high surface area e"en though the crystal structure of NaCoO2 is different from that of Co304 and it might be expected that there would be considerable loss of surface area on carrying out step (ii).
Step (iii) may be carried out by heating the Na MO2 with a melt of a soluble Li salt such as
LiNO3 and then removing excess Li salt by dissolution in water.
The LiMO2 product of the invention may be converted to LIMO2 where x is less than 1 as described in European Patent Application No 80300876-2, i.e. electrochemically by charging a non-aqueous cell represented as Li/electrolyte/LiMO2 towards a cell represented as Li/electrolyte/MO2.
LiMO2 prepared according to the invention and LIMO2 derived therefrom as above may be used as one or both of the solid-solution electrodes in an electrochemical cell where a liquid or solid electrolyte is arranged between the solid-solution electrodes.
The invention will now be particularly described, by way of example only, as follows where reference will be made to the accomFanying drawings, the sole figure of which (Ficj.
1) depicts values of Li + ion diffusion coeffic ent for compounds made according to this invention and also for compounds made as described in European Patent Application No 80300876-2.
Example
(i) CoC12.6H20 was dissolved in hot NaOH solution (-8M) by addition in small portions.
An approximate ratio of 1 litre of NaOH solution to 1 g of the Co salt was used. A blue solution was produced and this was cooled to room temperature and any solid residue filtered off. The blue solution was then dilutec with water using a water:solution ratio of about 3:1. The diluted solution was left for approximately 24 hours, in which time a gelatinous precipitate of Co304 had appearec and the blue colour had disappeared.
(ii) The Co304 precipitate was filtered off and dried and added to the stoichiometric amount of NaOH solution required to produce
NaCoO2. The mixture was heated to dryness in air at approximately 150 C to give NaCoC)2.
(iii) The NaCoO2 was converted to LiCoO2 by ion-exchange with a melt of LiNO3 at 300 C using an approximately 20 fold excel s of melt. This was cooled, the nitrate dissolved in water, and the LiCoO2 washed, filtered and dried.
The LiCoO2 product was examined by X-ray diffraction and was observed to give rise to broader peaks than those of LiCoO2 obtained by the abovementioned method described in
European Patent Application No 80300876-2. Thus, the LiCoO2 product has a higher surface area and hence a smaller particle size.
The electrochemical characteristics of the product were compared with those of LiCoO2 obtained as described in the above European patent application. Thus, in each case, the diffusion coefficient of the Li + ion was determined by a standard galvanostatic iterative titration method. The results are summarized in Fig. 1 where curve (a) indicates values for
LixCoO2 derived from the product of this example and curve (b) indicates values for Lix.
CoO2 derived from LiCoO2 obtained as described in the above European patent application. It will be seen that, for a given value of x, curve a always indicates a higher value of
Li+ ion diffusion coefficient. A higher diffusion coefficient implies a greater mobility of Li+ ions under an electrical potential. For a given overvoltage, this implies a greater current density and therefore power density of a
Li battery based on a product of the invention.
Claims (9)
1. A method of preparing a high surface area form of LiMO2, where M is a transition metal, which comprises the steps of
(i) precipitating a gelatinous form of an oxide of the transition metal M from a solution containing ions of the transition metal M;
(ii) converting the oxide prepared in step (i) to Na MO2; and
(iii) converting the NaMO2 to LiMO2 by ion exchange.
2. A method according to claim 1 wherein step (ii) is carried out by heating the oxide with a stoichiometric amount of NaOH.
3. A method according to either of the preceding claims wherein M is Fe, Co or Ni.
4. A method according to claim 3 wherein
M is Co and, in step (i), the solution contain
Co(ll) ions and the oxide is Co3O4.
5. A method according to any of the preceding claims wherein step (iii) is carried out by heating the NaMO2 with a melt of a soluble Li salt.
6. A method of preparing a high surface area form of LiCoO2 substantially as described herein with reference to the example.
7. A method according to any of the preceding claims wherein the high surface area form of LiMO2 produced thereby is converted electrnchemically to Li,MO2 where x is less than 1.
8. A high surface area form of LiMO2 or L#xMO2, wherein M and x are as defined herein, made by a method according to any of the preceding claims.
9. An electrochemical cell comprising a liquid or solid electrolyte arranged between solid-solution electrodes, one or both of which electrodes comprises a high surface area form of LiMO2 or LIMO2 according to claim 8.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB8134943A GB2087858B (en) | 1980-11-25 | 1981-11-19 | Reduction of so2 in polluted gases high surface area conductors |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB8037812 | 1980-11-25 | ||
| GB8134943A GB2087858B (en) | 1980-11-25 | 1981-11-19 | Reduction of so2 in polluted gases high surface area conductors |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| GB2087858A true GB2087858A (en) | 1982-06-03 |
| GB2087858B GB2087858B (en) | 1984-08-22 |
Family
ID=26277623
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB8134943A Expired GB2087858B (en) | 1980-11-25 | 1981-11-19 | Reduction of so2 in polluted gases high surface area conductors |
Country Status (1)
| Country | Link |
|---|---|
| GB (1) | GB2087858B (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0243926A1 (en) * | 1986-04-30 | 1987-11-04 | Sony Corporation | Organic electrolyte cell |
| GB2242566A (en) * | 1990-03-29 | 1991-10-02 | Dowty Electronic Components | Porous lithium electrode for battery |
| FR2704216A1 (en) * | 1993-04-23 | 1994-10-28 | Centre Nat Rech Scient | Electrode materials for rechargeable lithium batteries and their method of synthesis |
| EP0624552A1 (en) * | 1993-05-14 | 1994-11-17 | Moli Energy (1990) Limited | Novel method for preparing solid solution materials for secondary non-aqueous batteries |
| EP0728702A1 (en) * | 1995-02-27 | 1996-08-28 | Matsushita Electric Industrial Co., Ltd. | Lithium iron oxide, synthesis of the same, and lithium cell utilizing the same |
| WO1997005062A1 (en) * | 1995-08-02 | 1997-02-13 | Union Miniere S.A. | Synthesis of lithiated transition metal oxides |
| EP0798797A1 (en) * | 1996-03-26 | 1997-10-01 | Sharp Kabushiki Kaisha | Process for preparing positive electrode active materials, and nonaqueous secondary battery utilizing the same |
| EP0837037A1 (en) * | 1996-10-15 | 1998-04-22 | Matsushita Electric Industrial Co., Ltd. | Lithium iron oxide, method of its synthesis, and lithium battery using the same |
| FR2794741A1 (en) * | 1999-06-14 | 2000-12-15 | Commissariat Energie Atomique | MANGANESE LITHIUM OXIDES, PROCESS FOR THEIR PREPARATION AND THEIR USE AS A POSITIVE ELECTRODE IN A LITHIUM ACCUMULATOR |
-
1981
- 1981-11-19 GB GB8134943A patent/GB2087858B/en not_active Expired
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0243926A1 (en) * | 1986-04-30 | 1987-11-04 | Sony Corporation | Organic electrolyte cell |
| US4770960A (en) * | 1986-04-30 | 1988-09-13 | Sony Corporation | Organic electrolyte cell |
| GB2242566A (en) * | 1990-03-29 | 1991-10-02 | Dowty Electronic Components | Porous lithium electrode for battery |
| GB2242566B (en) * | 1990-03-29 | 1994-01-26 | Dowty Electronic Components | A battery |
| FR2704216A1 (en) * | 1993-04-23 | 1994-10-28 | Centre Nat Rech Scient | Electrode materials for rechargeable lithium batteries and their method of synthesis |
| WO1994025398A1 (en) * | 1993-04-23 | 1994-11-10 | Centre National De La Recherche Scientifique | Method of preparation of lithium and transition metal mixed oxides, oxides obtained and their use as electrode material |
| EP0624552A1 (en) * | 1993-05-14 | 1994-11-17 | Moli Energy (1990) Limited | Novel method for preparing solid solution materials for secondary non-aqueous batteries |
| EP0728702A1 (en) * | 1995-02-27 | 1996-08-28 | Matsushita Electric Industrial Co., Ltd. | Lithium iron oxide, synthesis of the same, and lithium cell utilizing the same |
| WO1997005062A1 (en) * | 1995-08-02 | 1997-02-13 | Union Miniere S.A. | Synthesis of lithiated transition metal oxides |
| EP0798797A1 (en) * | 1996-03-26 | 1997-10-01 | Sharp Kabushiki Kaisha | Process for preparing positive electrode active materials, and nonaqueous secondary battery utilizing the same |
| US5985488A (en) * | 1996-03-26 | 1999-11-16 | Sharp Kabushiki Kaisha | Process for preparing positive electrode active material, and nonaqueous secondary battery utilizing the same |
| EP0837037A1 (en) * | 1996-10-15 | 1998-04-22 | Matsushita Electric Industrial Co., Ltd. | Lithium iron oxide, method of its synthesis, and lithium battery using the same |
| US5955220A (en) * | 1996-10-15 | 1999-09-21 | Matsushita Electric Industrial Co., Ltd. | Lithium iron oxide, method of its synthesis, and lithium battery using the same |
| FR2794741A1 (en) * | 1999-06-14 | 2000-12-15 | Commissariat Energie Atomique | MANGANESE LITHIUM OXIDES, PROCESS FOR THEIR PREPARATION AND THEIR USE AS A POSITIVE ELECTRODE IN A LITHIUM ACCUMULATOR |
| WO2000076921A1 (en) * | 1999-06-14 | 2000-12-21 | Commissariat A L'energie Atomique | Lithium-containing manganese oxides, preparation method and use as positive electrode in a lithium cell battery |
Also Published As
| Publication number | Publication date |
|---|---|
| GB2087858B (en) | 1984-08-22 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| 732 | Registration of transactions, instruments or events in the register (sect. 32/1977) | ||
| 732E | Amendments to the register in respect of changes of name or changes affecting rights (sect. 32/1977) | ||
| 732E | Amendments to the register in respect of changes of name or changes affecting rights (sect. 32/1977) | ||
| PE20 | Patent expired after termination of 20 years |
Effective date: 20011118 |