WO1991002384A1 - Battery using manganese vanadate as active positive material - Google Patents

Battery using manganese vanadate as active positive material Download PDF

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Publication number
WO1991002384A1
WO1991002384A1 PCT/GB1990/001201 GB9001201W WO9102384A1 WO 1991002384 A1 WO1991002384 A1 WO 1991002384A1 GB 9001201 W GB9001201 W GB 9001201W WO 9102384 A1 WO9102384 A1 WO 9102384A1
Authority
WO
WIPO (PCT)
Prior art keywords
battery
manganese
manganese vanadate
vanadate
positive electrode
Prior art date
Application number
PCT/GB1990/001201
Other languages
French (fr)
Inventor
Robin John Neat
Marion Ruth Rance
Alan Hooper
Original Assignee
Dowty Electronic Components Limited
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.)
Filing date
Publication date
Application filed by Dowty Electronic Components Limited filed Critical Dowty Electronic Components Limited
Publication of WO1991002384A1 publication Critical patent/WO1991002384A1/en

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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
    • C01G45/00—Compounds of manganese
    • 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
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • 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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • H01M10/0587—Construction or manufacture of accumulators having only wound construction elements, i.e. wound positive electrodes, wound negative electrodes and wound separators
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • This invention relates to a battery and, in particular, to a battery which incorporates a new active material in the positive electrode thereof.
  • a battery having at least one electrochemical cell includes:
  • the positive electrode has an active material which includes, or comprises, Manganese Vanadate (M (V0 3 ) 2 ) .
  • the Manganese Vanadate (Mn(V0 3 ) 2 ) is formed by:
  • the resulting material formed is a mixture of essentially Vanadium Oxides and Manganese Vanadate (Mn(V0 3 ) 2 ).
  • the thermal decomposition of the mixture occurs by heating the mixture to a temperature of between 80°C and 150°C, and most preferably a temperature of between 100°C and 150°C.
  • V s O 3 Vanadium Oxide
  • V e 0 13 Vanadium Oxide
  • the amorphous state of the active conductive medium is not caused by the thermal conditions the mixture is subjected to, but by the actual reaction taking place.
  • the amorphous material formed is structurally unstable and will separate to form a two phase crystalline material. This being a distinct phase of Vanadium Oxides and a phase of Manganese Vanadate (Mn(V0 3 ) 2 ).
  • the negative electrode of the battery is a lithium metal or lithium alloy electrode.
  • the electrolyte used in a battery made in accordance with the present invention may be any suitable form of electrolyte material, solid or liquid.
  • FIG. 1 shows a schematic representation of a battery made in accordance with the present invention
  • Figure 2 is a sectional view of a section through the positive electrode of the battery, shown in Figure 1.
  • a battery 1 of conventional design comprises:
  • the cell comprises:
  • the cell has a basic configuration of
  • the battery is provided with two connections, a first connection (not shown) from the lithium electrode, the negative electrode 4, to a negative terminal (the outer cylindrical casing 2) , and a second connection 9 from the composite positive electrode 5 to a positive terminal 10.
  • the battery also includes two sealing insulating members 7, 8.
  • the first sealing insulating member 7 is disposed about the positive terminal 10 so as to insulate the negative terminal (the outer cylindrical casing 2) from the positive terminal 10. Further, the first sealing insulating member 7 acts as an atmospheric sealing member to seal the interior of the battery from the atmosphere, and thereby prevent the ingress of containments such as water vapour.
  • the second sealing insulating member 8 is disposed about the second connection 9 from the composite positive electrode 5 to the positive terminal 10 at a position between the positive terminal 10 and the cell. In this way the positive terminal 10 and the first sealing/insulating member 7 are insulated from the cell.
  • the electrolyte is a solid electrolyte which comprises polyethylene oxide (PEO) in which the Lithium salt Lithium Perchlorate (LiC10 4 ) is dispersed.
  • PEO polyethylene oxide
  • Lithium salt Lithium Perchlorate LiC10 4
  • a liquid electrolyte of propylene carbonate with ethylene carbonate may be used.
  • the Lithium salt Lithium Hexafluoroarsenate (LiAsF 6 ) may be dispersed in the electrolyte.
  • This electrode comprises:
  • the active material 12 is prepared by one of the methods described below, and comprises Manganese Vanadate (Mn(N0 3 ) 2 ) .
  • the composite positive electrode is manufactured by making a slurry mixture of the active material Manganese Vanadate (Mn(N0 3 ) 2 ) and applying this to the aluminium metal foil substrate 12. This is then dried leaving a coating of the active material on the foil substrate and so forming the composite positive electrode.
  • Mn(N0 3 ) 2 Manganese Vanadate
  • Manganese Vanadate (Mn(N0 3 ) 2 ) is forming, as followed:
  • V S 0 3 Vanadium Oxide
  • Mn(N0 3 ) 2 aqueous solution of Manganese Nitrate
  • V 6 0 13 crystalline Vanadium Oxide
  • the Vanadium Oxides and the Manganese Vanadate (Mn(V0 3 ) 2 ) formed by the above mentioned preparation method for Manganese Vanadate (Mn(V0 3 )s_) are formed as two separate and distinct phases.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

A battery (1) which has at least one electrochemical cell which includes: a negative electrode (4), an electrolyte and a positive electrode(5). The positive electrode has an active material which includes, or comprises, Manganese Vanadate (Mn(VO3)2). A method of manufacturing the Manganese Vanadate is also disclosed.

Description

BATTERY USING MANGANESE VANADATE AS ACTIVE POSITIVE MATERIAL
This invention relates to a battery and, in particular, to a battery which incorporates a new active material in the positive electrode thereof.
In accordance with the present a battery having at least one electrochemical cell, includes:
a negative electrode;
an electrolyte;
and - a positive electrode;
wherein the positive electrode has an active material which includes, or comprises, Manganese Vanadate (M (V03)2) .
In a preferred arrangement of the present invention the Manganese Vanadate (Mn(V03)2) is formed by:
1) mixing an aqueous solution of Manganese Nitrate (Mn(N03)2) with Vanadium Oxide ~ (V60X3) so as to form a surface coating on the Vanadium Oxide;
2) thermally decomposing the mixture so as to form a homogeneous amorphous compound having the arbitrary stoichiometry Mn02/Vβ013;
3) forming a cell with the amorphous compound as the positive electrode and charging and discharging the cell a number of times;
and 4) separating the Manganese Vanadate
(Mn(V03)2) formed from the resulting material.
With the above method the resulting material formed is a mixture of essentially Vanadium Oxides and Manganese Vanadate (Mn(V03)2).
Preferably, the thermal decomposition of the mixture occurs by heating the mixture to a temperature of between 80°C and 150°C, and most preferably a temperature of between 100°C and 150°C.
The thermal decomposition of the materials under the above conditions will cause the Manganese Nitrate (Mn(N03)2( and the Vanadium Oxide (V6013) to form a homogeneous amorphous compound of arbitrary stoichiometry Mn02/VβO__.3 (Manganese Dioxide/Vanadium Oxide) with the evolving of Nitrogen Dioxide (N02).
Previously, it has been advanced that Vanadium Oxide (VsO 3) will restructure itself from a crystalline structure to an amorphous material under a thermal influence. However, a control test of Vanadium Oxide (Ve013) under the conditions of the present invention showed that no such restructuring occurred. Therefore, the amorphous state of the active conductive medium is not caused by the thermal conditions the mixture is subjected to, but by the actual reaction taking place. Under certain conditions the amorphous material formed is structurally unstable and will separate to form a two phase crystalline material. This being a distinct phase of Vanadium Oxides and a phase of Manganese Vanadate (Mn(V03)2).
The conditions which readily facilitate the above separation of the amorphous material are:
1) time,
and 2) elevated temperatures.
Preferably, the negative electrode of the battery is a lithium metal or lithium alloy electrode.
The electrolyte used in a battery made in accordance with the present invention may be any suitable form of electrolyte material, solid or liquid.
The invention also includes the use of Manganese Vanadate in a battery made in accordance with the present invention. The invention will now be described by way of example with reference to the accompanying drawings, in which:
Figure 1 shows a schematic representation of a battery made in accordance with the present invention;
and Figure 2 is a sectional view of a section through the positive electrode of the battery, shown in Figure 1.
Now referring to Figure 1 of the drawings, a battery 1 of conventional design comprises:
- an outer cylindrical casing 2;
and - a cell of wound construction contained within the outer cylindrical casing 2.
The cell comprises:
an elongate strip 4 of Lithium metal, which forms the negative electrode of the battery;
a composite positive electrode 5 having an active material comprising Manganese Vanadate (Mn(N03)2) ;
two insulating separator strips 6 disposed one on either side of the composite positive electrode 5;
and - a solid electrolyte.
The cell has a basic configuration of
negative electrode 4 separator 6 positive electrode 5 separator 6,
which is wound so that it can be disposed in the cylindrical casing 2.
Further, the battery is provided with two connections, a first connection (not shown) from the lithium electrode, the negative electrode 4, to a negative terminal (the outer cylindrical casing 2) , and a second connection 9 from the composite positive electrode 5 to a positive terminal 10.
The battery also includes two sealing insulating members 7, 8.
The first sealing insulating member 7 is disposed about the positive terminal 10 so as to insulate the negative terminal (the outer cylindrical casing 2) from the positive terminal 10. Further, the first sealing insulating member 7 acts as an atmospheric sealing member to seal the interior of the battery from the atmosphere, and thereby prevent the ingress of containments such as water vapour.
The second sealing insulating member 8 is disposed about the second connection 9 from the composite positive electrode 5 to the positive terminal 10 at a position between the positive terminal 10 and the cell. In this way the positive terminal 10 and the first sealing/insulating member 7 are insulated from the cell.
In this embodiment of the invention the electrolyte is a solid electrolyte which comprises polyethylene oxide (PEO) in which the Lithium salt Lithium Perchlorate (LiC104) is dispersed.
In an alternative arrangement a liquid electrolyte of propylene carbonate with ethylene carbonate (PC/EC) may be used. In this case the Lithium salt. Lithium Hexafluoroarsenate (LiAsF6) may be dispersed in the electrolyte.
Now referring to Figure 2 of the drawings, the composite positive electrode 5 is shown. This electrode comprises:
- an aluminium foil substrate 11;
and - a coating of active material 12.
The active material 12 is prepared by one of the methods described below, and comprises Manganese Vanadate (Mn(N03)2) .
The composite positive electrode is manufactured by making a slurry mixture of the active material Manganese Vanadate (Mn(N03)2) and applying this to the aluminium metal foil substrate 12. This is then dried leaving a coating of the active material on the foil substrate and so forming the composite positive electrode.
The active material Manganese Vanadate (Mn(N03)2) is forming, as followed:
- mixing Vanadium Oxide (VS03) with an aqueous solution of Manganese Nitrate (Mn(N03)2) so that the aqueous Manganese Nitrate (Mn(N03)2) forms a surface coating on the crystalline Vanadium Oxide (V6013);
thermally decomposing by heating to a temperature of 120°C for 3 hours the above mixture so that a homogeneous amorphous material having the arbitrary stoichiometry Mn02/Vs013 (Manganese Dioxide/Vanadium Oxide) is formed;
- pausing the homogeneous amorphous material, by utilising the effects of time and temperature to separate into two distinct phases, one of Vanadium Oxides and one of Manganese Vanadate (Mn(V03)2);
and - separating the Manganese Vanadate
(Mn(V03)2) from the Vanadium Oxides.
The Vanadium Oxides and the Manganese Vanadate (Mn(V03)2) formed by the above mentioned preparation method for Manganese Vanadate (Mn(V03)s_) are formed as two separate and distinct phases.

Claims

1. A battery having at least one elctrochemical cell, including:
- a negative electrode;
- an electrolyte;
and - a positive electrode;
wherein the positive electrode has an active material which includes, or comprises. Manganese Vanadate (Mn(V03)2) .
2. A battery as claimed in claim 1, wherein the Manganese Vanadate (Mn(V03)2)
1) mixing an aqueous solution of Manganese Nitrate (Mn(N03)2) with Vanadium Oxide (Vs013) so as to form a surface coating on the Vanadium Oxide;
2) thermally decomposing the mixture so as to form a homogeneous amorphous compound having the arbitrary stoichiometry Mn02/V60 3;
3) causing the homogeneous amorphous material, by utilising the effects of time and temperature to separate into two distinct phases, one of Vanadium Oxides and one of Manganese Vanadate (Mn(V03)2);
and 4) separating the Manganese Vanadate
(Mn(V03)2) formed from the resulting material.
3. A battery as claimed in claim 2, wherein the thermal decomposition of the mixture occurs by heating the mixture to a temperature of 120°C for a period of 3 hours.
4. A battery as claimed in any one of the preceding claims, wherein the negative electrode of the battery is a lithium metal or lithium alloy electrode.
5. A battery as claimed in any one of the preceding claims, wherein the electrolyte contains a lithium salt.
6. The use of Manganese Vanadate (Mn(V03)2) in a battery as claimed in any one of the preceding claims.
PCT/GB1990/001201 1989-08-04 1990-08-02 Battery using manganese vanadate as active positive material WO1991002384A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB8917913.9 1989-08-04
GB898917913A GB8917913D0 (en) 1989-08-04 1989-08-04 A battery

Publications (1)

Publication Number Publication Date
WO1991002384A1 true WO1991002384A1 (en) 1991-02-21

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Application Number Title Priority Date Filing Date
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WO (1) WO1991002384A1 (en)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1994029914A1 (en) * 1993-06-14 1994-12-22 Valence Technology, Inc. Vanadium oxide cathode active material and method of making same
WO1994029913A1 (en) * 1993-06-14 1994-12-22 Valence Technology, Inc. Vanadium oxide cathode active material and method of making same
CN104118912A (en) * 2014-08-14 2014-10-29 安徽工业大学 Method for preparing manganese vanadate nano-ribbons
CN113856732A (en) * 2021-11-08 2021-12-31 西北大学 Lamellar flower-shaped Mn (VO)3)2Composite g-C3N4Photocatalyst and preparation method and application thereof
CN114560503A (en) * 2022-01-21 2022-05-31 武汉科技大学 Preparation method of manganese vanadate and manufacturing method of ammonia sensor
CN114602458A (en) * 2022-03-22 2022-06-10 江苏理工学院 Mn (VO)3)2/V2O5Catalyst, preparation method and application thereof

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104528830B (en) * 2014-12-03 2016-10-05 石家庄学院 A kind of method synthesizing manganese vanadate nano-micrometre material
CN110668505B (en) * 2019-09-24 2022-04-26 烟台大学 Cobalt-containing two-dimensional accordion-shaped nanosheet material and preparation method and application thereof

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3681143A (en) * 1970-09-03 1972-08-01 Mallory & Co Inc P R Lithium-metal vanadate organic electrolyte cell

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5539146A (en) * 1978-09-14 1980-03-18 Hitachi Ltd Primary cell
US4310609A (en) * 1979-12-17 1982-01-12 Wilson Greatbatch Ltd. Metal oxide composite cathode material for high energy density batteries

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3681143A (en) * 1970-09-03 1972-08-01 Mallory & Co Inc P R Lithium-metal vanadate organic electrolyte cell

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1994029914A1 (en) * 1993-06-14 1994-12-22 Valence Technology, Inc. Vanadium oxide cathode active material and method of making same
WO1994029913A1 (en) * 1993-06-14 1994-12-22 Valence Technology, Inc. Vanadium oxide cathode active material and method of making same
CN104118912A (en) * 2014-08-14 2014-10-29 安徽工业大学 Method for preparing manganese vanadate nano-ribbons
CN113856732A (en) * 2021-11-08 2021-12-31 西北大学 Lamellar flower-shaped Mn (VO)3)2Composite g-C3N4Photocatalyst and preparation method and application thereof
CN114560503A (en) * 2022-01-21 2022-05-31 武汉科技大学 Preparation method of manganese vanadate and manufacturing method of ammonia sensor
CN114602458A (en) * 2022-03-22 2022-06-10 江苏理工学院 Mn (VO)3)2/V2O5Catalyst, preparation method and application thereof
CN114602458B (en) * 2022-03-22 2023-05-26 江苏理工学院 Mn (VO 3 ) 2 /V 2 O 5 Catalyst, preparation method and application thereof

Also Published As

Publication number Publication date
GB2235567A (en) 1991-03-06
GB9016956D0 (en) 1990-09-19
GB8917913D0 (en) 1989-09-20
GB2235567B (en) 1994-02-09

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