GB2242440A - Electrodeposition of lithium from organic solvent. - Google Patents

Electrodeposition of lithium from organic solvent. Download PDF

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Publication number
GB2242440A
GB2242440A GB9104952A GB9104952A GB2242440A GB 2242440 A GB2242440 A GB 2242440A GB 9104952 A GB9104952 A GB 9104952A GB 9104952 A GB9104952 A GB 9104952A GB 2242440 A GB2242440 A GB 2242440A
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GB
United Kingdom
Prior art keywords
lithium
bath
cathode
solution
supplementary
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
Application number
GB9104952A
Other versions
GB9104952D0 (en
GB2242440B (en
Inventor
Paul Radmall
Christine Ruth Jarvis
Nicholas John Williamson
Peter Malcolm Cooke
David John Whittaker
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dowty Electronic Components Ltd
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Dowty Electronic Components Ltd
Priority date (The priority date 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 date listed.)
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Publication date
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Publication of GB9104952D0 publication Critical patent/GB9104952D0/en
Publication of GB2242440A publication Critical patent/GB2242440A/en
Application granted granted Critical
Publication of GB2242440B publication Critical patent/GB2242440B/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

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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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0438—Processes of manufacture in general by electrochemical processing
    • H01M4/045—Electrochemical coating; Electrochemical impregnation
    • H01M4/0452—Electrochemical coating; Electrochemical impregnation from solutions
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D21/00—Processes for servicing or operating cells for electrolytic coating
    • C25D21/16—Regeneration of process solutions
    • C25D21/18—Regeneration of process solutions of electrolytes
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/54—Electroplating: Baths therefor from solutions of metals not provided for in groups C25D3/04 - C25D3/50
    • 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
    • H01M4/04—Processes of manufacture in general
    • H01M4/0438—Processes of manufacture in general by electrochemical processing
    • 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
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • 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
    • 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)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electroplating And Plating Baths Therefor (AREA)

Abstract

A process for the electrodeposition of lithium which comprises plating onto a primary cathode in a bath of lithium ions in solution with an organic solvent, and using a supplementary cathode to neutralise by-products detrimental to the process. The supplementary cathode is aluminium and may be used in the same bath or a connected bath. Lithium chloride and lithium hexafluoroarsenate provide the lithium ions. Additionally, a bath may comprise a solution of lithium ions in dimethyl sulphoxide as the organic solvent.

Description

ELECTRODEPOSITION OF LITHIUM Technical Field This invention relates to the electrodeposition of lithium and baths therefor.
For a variety of applications, in particular in battery technology, there is a demand for uniform, good quality lithium or lithium coated materials.
Use of electrodeposition techniques to produce such materials have hitherto not proved to be a practical or an economical proposition because of the general difficulties in finding suitable feed stock substances for an electrodeposition bath.
The most widely available lithium salts such as lithium chloride or lithium carbonate are very insoluble in suitable solvents and the salts which are more soluble tend to be very expensive.
It has been found that a bath comprising a solution of lithium ions, for example lithium chloride, tends to deteriorate somewhat and provide poor quality deposits after a relatively short bath life and also that it is not possible to arrest this deterioration by regeneration of the lithium ion concentration.
Disclosure of the Invention The invention is concerned with the provision of suitable lithium electrodeposition processes and baths which can in general be operated relatively inexpensively and at comparatively low temperatures.
According to one aspect, the invention consists in a process for the electrodeposition of lithium which comprises plating onto a primary cathode in a bath of lithium ions in solution with an organic solvent, and using a supplementary cathode which removes or renders harmless by-products formed in the process which might be detrimental to the process or the deposit.
It has been found that a supplementary cathode of aluminium is especially useful. The supplementary cathode may comprise pure aluminium, an aluminium alloy or may be a substrate having an aluminium or an aluminium alloy surface.
The supplementary cathode may be used continuously in the electrodeposition process or alternatively it may be used occasionally either together with the primary cathode or in the absence of the primary cathode, for example after a particular individual primary cathode has been successfully plated. In any event, the supplementary cathode may be part of the same cell as the primary cathode, i.e. using a common anode, or may be in a separate cell through which the electrolyte is circulated.
The anode or anodes are inert, insoluble anodes composed of platinum or other suitable material.
Some lithium deposition may take place on the aluminium supplementary cathode. The deposited metal can be recovered by causing it to be used as an anode from time to time.
Lithium chloride may be used to provide the lithium ions in solution with the organic solvent, and preferably, the lithium chloride is used in combination with a further source of lithium ions, for example lithium hexafluoroarsenate. It has been found that a mixed bath of lithium chloride and lithium hexafluoroarsenate provides lithium deposits of enhanced quality. Furthermore, regeneration of the bath, and hence improved bath life, may be effected solely or mainly by means of the addition of lithium chloride which in general is one of the least expensive forms of lithium salt commercially available.
The organic solvent preferably comprises dimethyl sulphoxide, used either alone or in combination with one or more other solvents present as minor constituents.
According to another aspect, the present invention consists in a process for the electrodeposition of lithium onto a cathode in a bath comprising a solution of lithium ions in dimethyl sulphoxide.
This process may employ either an inert, insoluble anode, or an active, soluble anode, for example a lithium anode, in which case, the anode will be a source of lithium ions and additional replenishment of the bath will not generally be necessary. The lithium ions are preferably provided by lithium chloride or lithium chloride in combination with lithium hexafluoroarsenate.
A general benefit of the processes of the invention is that they may generally be operated at relatively low temperatures. Typically a temperature of 250C has been found useful.
In one example of the electrodeposition process according to the invention, a plating bath comprises a concentration of between 0.1 and 2 molar, typically 0.6 molar, of lithium chloride, and a concentration of between 0.08 and 0.5 molar, typically 0.1 molar, of lithium hexafluoroarsenate in solution with dimethyl sulphoxide. The bath has a temperature of 250C. An article to be plated with lithium is immersed in the bath and a voltage applied between it as the cathode, and a platinum anode so as to cause lithium to be deposited on the article. The current density is preferably maintained in the range from 2 to 20 mA/cm2.A supplementary cathode of pure aluminium is occasionally immersed in the bath when the plating process is inoperative, for example, between the plating of individual articles, and a voltage is applied between it and the anode so as to remove by-products -of the plating process by deposition on the supplementary cathode. The supplementary cathode is removed before the plating process is resumed. The bath can be regenerated by the addition of lithium chloride as necessary.
In a second example of a process according to the invention, a plating bath comprises the same solution of lithium chloride and lithium hexafluoroarsenate in dimethyl sulphoxide as described in the first example, and the temperature of the bath and current density used are the same. However, the solution is circulated from the one bath containing the primary cathode to a second bath containing the supplementary cathode in which the by-products are neutralised, the solution then being re-circulated back to the first bath. Each bath is provided with a separate platinum anode, and voltages are applied between the cathodes and anodes as required for simultaneous continuous or intermittent plating and neutralisation of the by-products.
In a third example of a process according to the invention, a plating bath comprises the same solution of lithium chloride and lithium hexafluoroarsenate in dimethyl sulphoxide as described in the first example above. The bath has a temperature of 250C. An article to be plated with lithium is immersed in the bath and a voltage applied between it as the cathode, and an anode so as to cause lithium to be deposited on the article. The current density is preferably maintained in the range from 2 to 20 mA/cm2. The ~ anode may be a platinum anode or a lithium anode.
Lithium ions are replenished in the bath by the addition of lithium chloride as necessary, although this may not be necessary if a lithium anode is employed.

Claims (37)

1. A process for the electrodeposition of lithium comprising providing a solution of lithium ions in an organic solvent, providing a primary cathode in the solution and applying a voltage between it and an inert anode so as to plate the primary cathode with lithium, and providing a supplementary cathode in the solution and applying a voltage between it and an inert anode, the composition of the supplementary cathode being such as to react with and neutralise by-products which would otherwise be detrimental to the lithium plating process.
2. A process as claimed in claim 1 in which the supplementary cathode comprises aluminium.
3. A process as claimed in claim 1 or claim 2 in which lithium chloride is used to provide lithium ions in solution.
4. A process as claimed in claim 3 in which the concentration of lithium chloride is 0.1 to 2 molar.
5. A process as claimed in claim 3 or 4 in which lithium hexafluoroarsenate is used in combination with the lithium chloride to provide lithium ions in solution.
6. A process as claimed in claim 5 in which the concentration of lithium hexafluoroarsenate is 0.08 to 0.5 molar.
7. A process as claimed in any one of claims 3 to 6 in which the bath is replenished by the addition of lithium chloride as the process proceeds.
8. A process as claimed in any one of the preceding claims in which the organic solvent comprises dimethyl sulphoxide.
9. A process as claimed in any one of the preceding claims in which the primary cathode and supplementary cathode are provided in separate baths with the solution circulated between the two.
10. A process as claimed in any one of the claims 1 to 8 in which the primary cathode and supplementary cathode are provided in one and the same bath with a common anode.
11. A process as claimed in any one of claims 9 or 10 in which the primary cathode and supplementary cathode are used simultaneously.
12. A process as claimed in claim 11 in which the primary cathode and supplementary cathode are used each at different times.
13. A process as claimed in claim 12 in which the supplementary cathode is used to neutralise by-products in the bath between the plating of successive cathodes.
14. A process as claimed in any one of the preceding claims in which the supplementary cathode is used occasionally as an anode in the solution to recover lithium deposited on it.
15. A process for the electrodeposition of lithium which comprises plating onto a cathode in a bath comprising a solution of lithium ions in dimethyl sulphoxide.
16. A process as claimed in claim 15 in which lithium ions are provided by lithium chloride.
17. A process as claimed in claim 16 in which lithium ions are provided by lithium hexafluoroarsenate.
18. A process as claimed in any one of claims 15 to 17 in which an inert anode is provided in the bath.
19. A process as claimed in any one of claims 15 to 18 in which the lithium ions are replenished by the addition of lithium chloride to the bath.
20. A process as claimed in any one of claims 15 to 17 in which the bath is provided with an anode which comprises lithium so as to replenish lithium ions in the bath.
21. A process as claimed in any one of the preceding claims in which the current density for the cathode or cathodes is from 2 to 20 mA/cm2.
22. A bath for the electrodeposition of lithium comprising lithium ions in solution with an organic solvent, a primary cathode in the bath which is to be plated with lithium, and a supplementary cathode which is to neutralise by-products in the bath.
23. A bath as claimed in claim 22 in which the supplementary cathode comprises aluminium.
24. A bath as claimed in claim 22 or 23 which contains lithium chloride in solution.
25. A bath as claimed in claim 24 in which the concentration of lithium chloride is 0.1 to 2 molar.
26. A bath as claimed in claim 24 or 25 which contains lithium hexafluoroarsenate.
27. A bath as claimed in claim 26 in which the concentration of hexafluoroarsenate is 0.08 to 0.5 molar.
28. A bath as claimed in any one of claims 22 to 27 in which the organic solvent comprises dimethyl sulphoxide.
29. A bath as claimed in any one of claims 22 to 28 in which the primary cathode and supplementary cathode are provided in one and the same bath with a common anode which is inert and insoluble in the solution.
30. A bath as claimed in any one of claims 22 to 28 in which the primary cathode and supplementary cathode are provided in separate baths connected so that the solution can be circulated between them.
31. A bath for the electrodeposition of lithium comprising a solution of lithium ions in dimethyl sulphoxide.
32. A bath as claimed in claim 31 which contains lithium chloride in solution.
33. A bath as claimed in claim 31 or 32 which contains lithium hexafluoroarsenate.
34. A bath as claimed in any one of claims 31 to 33 in which an inert and insoluble anode is provided in the bath.
35. A bath as claimed in any one of claims 31 to 33 in which a lithium anode is provided in the bath.
36. A process for the electrodeposition of lithium substantially as herein described with reference to the accompanying examples.
37. A bath for the electrodeposition of lithium substantially as herein described with reference to the accompanying examples.
GB9104952A 1990-03-09 1991-03-08 Electrodeposition of lithium Expired - Fee Related GB2242440B (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
GB909005337A GB9005337D0 (en) 1990-03-09 1990-03-09 Electrodeposition of lithium

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GB9104952D0 GB9104952D0 (en) 1991-04-24
GB2242440A true GB2242440A (en) 1991-10-02
GB2242440B GB2242440B (en) 1994-07-20

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GB9104952A Expired - Fee Related GB2242440B (en) 1990-03-09 1991-03-08 Electrodeposition of lithium

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2383337A (en) * 2001-12-21 2003-06-25 Accentus Plc Electroplating plant and method
EP3316347A1 (en) 2016-10-28 2018-05-02 Robert Bosch GmbH Secondary battery and method for producing the same
WO2023284918A3 (en) * 2021-07-16 2023-05-19 RENA Technologies GmbH Methods and devices for enriching a substrate with an alkali metal, and electrolyte

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
IL109845A (en) * 1994-06-01 1998-08-16 Tadiran Ltd Rechargeable electrochemical cell

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1045228A (en) * 1964-10-13 1966-10-12 American Cyanamid Co Non-aqueous solvents, electrodeposition and electrodissolution of metals therein andelectrochemical cells containing solutions of salts in non-aqueous solvents as electrolyte
GB1574987A (en) * 1977-08-15 1980-09-17 Pitt Metals & Chemicals Process for the control of alkali metal hydroxide in electro-plating baths
US4229280A (en) * 1978-04-13 1980-10-21 Pitt Metals & Chemicals, Inc. Process for electrodialytically controlling the alkali metal ions in a metal plating process
US4713151A (en) * 1986-10-31 1987-12-15 Amoco Corporation Electrodeposition of lithium
US4906340A (en) * 1989-05-31 1990-03-06 Eco-Tec Limited Process for electroplating metals
US4933051A (en) * 1989-07-24 1990-06-12 Omi International Corporation Cyanide-free copper plating process

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4167458A (en) * 1978-03-28 1979-09-11 Union Carbide Corporation Lithium ion-containing organic electrolyte

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1045228A (en) * 1964-10-13 1966-10-12 American Cyanamid Co Non-aqueous solvents, electrodeposition and electrodissolution of metals therein andelectrochemical cells containing solutions of salts in non-aqueous solvents as electrolyte
GB1574987A (en) * 1977-08-15 1980-09-17 Pitt Metals & Chemicals Process for the control of alkali metal hydroxide in electro-plating baths
US4229280A (en) * 1978-04-13 1980-10-21 Pitt Metals & Chemicals, Inc. Process for electrodialytically controlling the alkali metal ions in a metal plating process
US4713151A (en) * 1986-10-31 1987-12-15 Amoco Corporation Electrodeposition of lithium
US4906340A (en) * 1989-05-31 1990-03-06 Eco-Tec Limited Process for electroplating metals
US4933051A (en) * 1989-07-24 1990-06-12 Omi International Corporation Cyanide-free copper plating process
GB2234260A (en) * 1989-07-24 1991-01-30 Omi Int Corp Cyanide-free copper electroplating process

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2383337A (en) * 2001-12-21 2003-06-25 Accentus Plc Electroplating plant and method
EP3316347A1 (en) 2016-10-28 2018-05-02 Robert Bosch GmbH Secondary battery and method for producing the same
DE102016221256A1 (en) 2016-10-28 2018-05-03 Robert Bosch Gmbh Secondary battery and method for producing such
WO2023284918A3 (en) * 2021-07-16 2023-05-19 RENA Technologies GmbH Methods and devices for enriching a substrate with an alkali metal, and electrolyte

Also Published As

Publication number Publication date
GB9005337D0 (en) 1990-05-02
GB9104952D0 (en) 1991-04-24
GB2242440B (en) 1994-07-20
WO1991014025A1 (en) 1991-09-19

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PCNP Patent ceased through non-payment of renewal fee

Effective date: 19950308