CA2004744C - Lithium primary cell, cathode active material therefor, and method for manufacturing manganese dioxide for cathode active material - Google Patents
Lithium primary cell, cathode active material therefor, and method for manufacturing manganese dioxide for cathode active materialInfo
- Publication number
- CA2004744C CA2004744C CA002004744A CA2004744A CA2004744C CA 2004744 C CA2004744 C CA 2004744C CA 002004744 A CA002004744 A CA 002004744A CA 2004744 A CA2004744 A CA 2004744A CA 2004744 C CA2004744 C CA 2004744C
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- Prior art keywords
- manganese dioxide
- active material
- cathode active
- electrolyte
- primary cell
- Prior art date
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Classifications
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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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/21—Manganese oxides
-
- 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
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
-
- 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
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- 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)
- Inorganic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
A lithium primary cell includes a cathode active material containing 0.05 to 2.0 parts by weight of phosphorus with respect to 100 parts by weight of manganese dioxide. A cathode active material for a lithium primary cell contains 0.05 to 2.0 parts by weight of phosphorus with respect to 100 parts by weight of manganese dioxide. A method for manufacturing electrolytic manganese dioxide comprises adding at least one member selected from the group consisting of phosphoric acid, phosphorous acid, hypophosphorous acid and compounds thereof to the electrolyte during the manufacture of electrolytic manganese dioxide using manganese sulfate and a sulfuric acid solution as the electrolyte.
Description
2~0$ 7~4 TITLE OF THE INVENrl~ION
Lithium Primary Cell, Cathode Active Material Therefor, and Method for Manufacturing Manganese Dioxide for Cathode ~ctive Material BACKGROUND OF THE INVENTION:
Field of the Invention The present invention relates to a lithium primary cell using lithium or a lithium alloy as an anode active material and manganese dioxide as a cathode active material, a cathode active material therefor, and a method for manufacturing manganese dioxide for the cathode active materia 1 .
Description of the Prior Art Manganese dioxide and carbon fluoride are known as typical examples of a cathode active material of a lithium primary cell and are already commercially available.
Of these cathode active materials, manganese dioxide is advantageous since it has a good storage stability and is inexpensive.
A lithium primary cell using manganese dioxide as a cathode active material is currently applied to a camera and the like. As a multi-function of a camera has progressed, a demand has arisen for a lithium primary cell to have a high discharge voltage. A large discharge capacity, i.e., a long discharge time is also demanded for the lithium primary cell. No lithium primary cell, however, which can satisfy both the re~uirements with a good balance, has been proposed.
, ~ - 2 - 2G~474~
SUMMARY OF THE INVENTION:
The present invention has been made in consideration of the above situation and is intended to provide a lithium primary cell which uses manganese dioxide as a cathode active material and achieves both a high discharge voltage and a long discharge time, a cathode active material therefor, and a method for manufacturing manganese dioxide for the cathode active material.
The above object of the present invention is achieved by adding 0.05 to 2.0 parts by weight of phosphorus to 100 parts by weight of manganese dioxide and using the resultant material as a cathode active material of a lithium primary cell.
According to the present invention, manganese dioxide containing phosphorus is used as a cathode active material. When this cathode active material is used for manufacturing a lithium primary cell, both a high discharge voltage and a long discharge time are achieved.
In this case, the content of phosphorus is generally 0.05 to 2.0 parts by weight with respect to 100 parts by weight of manganese dioxide. If the phosphorus content is less than 0.05 parts by weight with respect to 100 parts by weight of manganese dioxide, no sufficient addition effect is obtained in terms of discharge characteristics of a manufactured lithium primary cell. If the phosphorus content exceeds 2.0 parts by weight, discharge characteristics of manganese dioxide of a manufactured lithium primary cell are degraded.
2~,~,4 144 Such manganese dioxide containing phosphorus is manufactured by, e.g., the following method.
That is, manganese dioxide containing phosphorus is manufactured by adding phosphoric acid, phosphorus acid, hypophosphorous acid, or a derivative thereof to an electrolyte during the manufacture of electrolytic manganese dioxide using manganese sulfate and a sulfuric acid solution as the electrolyte.
In this manufacturing method, manganese sulfate and a sulfuric acid solution are used as an electrolyte. Generally, in this electrolyte, a manganese concentration is 20 to S0 g/~, and a sulfuric acid concentration is 30 to 80 g/e. In addition, as electrodes, titanium or the like is used as a cathode, and carbon or the like is used as an anode.
Electrolytic conditions for electrolytic manganese dioxide are generally a bath temperature of 90~ to 100~C and a current density of 50 to 100 A/m2.
In this manufacturing method, phosphoric acid, phosphorous acid, hypophosphorous acid, or a derivative thereof is added to the electrolyte. Examples of the derivative are a sodium salt, a potassium salt, and the like. The phosphoric acid compound or the like is uniformly added together with a manganese sulfate supply solution from an upper portion of an electrolytic cell to between electrode plates.
2~04 744 The concentration of the phosphoric acid compound or the like in the electrolyte is set to be 0.1 to 3.0 g/~, and the electrolytic conditions are adjusted so that phosphorus is contained in an amount falling within the above range in the manufactured electrolytic manganese dioxide.
The electrolytic manganese dioxide manufactured as descr bed above has a large specific surface area of 40 to 150 m /g. If the specific surface area of electrolytic manganese dioxide is smaller than the above value, reaction area with respect to an electrolyte is small and load discharge performance is weak when this electrolytic manganese dioxide is used as a cathode active material to manufacture a lithium primary cell. If the specific surface area of electrolytic manganese dloxide exceeds the above value, a cathode agent becomes bulky. The specific surface area of electrolytic manganese dioxide can be adjusted by arbitrarily selecting the type or content of the phosphoric acid compound.
A lithium primary cell, manufactured under normal conditions by using electrolytic manganese dioxide containing phosphorus as a cathode active material and lithium or a lithium alloy such as lithium-aluminum as an anode, has a higher discharge voltage and a longer discharge time than those of a conventional lithium primary cell.
BRIEF DESCRIPTION OF T~E DRAWINGS:
Fig.-1 is a schematic sectional view for explaining a test cell used in examples and a comparative example; and 2t)C4 ~44 Figs. 2 and 3 are graphs each showing a relationship between a voltage and a continuous discharge time in the examples and comparative example.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT:
The present invention will be described in detail below by way of its examples.
ExamPle 1 A titanium plate as a cathode and a graphite plate as an anode were alternately suspended in an electrolytic cell having a volume of 3~ and equipped with a heating apparatus, and an addition tube was connected to the bottom portion of the electrolytic cell to add an electrolytic supply solution composed of manganese sulfate and a phosphoric acid solution.
The electrolytic supply solution was adjusted so that 0.5 g/e of sulfuric acid were contained in the manganese sulfate solution.
When electrolysis was performed by supplying the supply solution in the electrolytic cell, the composition of the electrolyte was adjusted so that 50 g/~ of manganese and 30 g/e of sulfuric acid were contained. Electrolysis was performed at a bath temperature of 95 il~C and a current density of 100 A/m2 .
After electrolysis was finished, the cathode plate on which electrolytic manganese dioxide was electro-deposited was removed from the cell and subjected to a normal post-treatment, and the specific surface area of the obtained electrolytic manganese dioxide was measured. The measurement results are listed in Table 1.
~ ~ .~ s. ,, 2 0 ~, 4 1 4 4 A heat treatment was performed at 400~C for three hours, 0.135 g of the obtained electrolytic manganese dioxide were measured, and 0.09 g of graphite and 0.06 g of a tetrafluoroethylene resin were mixed therewith. The resultant mixture was pressure-molded at 3 t/cm2 to prepare a cathode mixture. Note that the manganese dioxide, the graphite and the tetrafluoroethylene were predried and mixed.
The prepared cathode mixture was used to form a test cell as shown in Fig. 1, and a 2.5 KQ continuous discharge test was performed at 20~C. All these operations were performed in a dry box in an argon atmosphere. The electrolyte was prepared by dissolving 1 mol/e of lithium perchlorate in a 1:1 solvent mixture of propylenecarbonate and l,2-dimethoxyethane.
A reagent used in this test was dried by a conventional method. In addition, the anode was formed by punching a metal lithium sheet to have the same diameter as that of the cathode mixture.
In the test cell shown in Fig. 1, reference numeral 1 denotes an anode terminal for externally extracting a current; and 2, insulating members made of a Teflon (trademark) resin. The insulating members 2 are threadably engaged with each other to close the cell. Reference numeral 3 denotes an anode platei 4, a crimped metal lithium sheet (anode)i 5, a separator made of a non-woven fabric; 6, a cathode mixture lormed by the above method; and 7, a stainless steel cathode.
A discharge test was performed by using the above test cell. The obtained relationship between a voltage and a continuous discharge time is shown in Fig. 2.
Examples 2 and 3 By using an apparatus similar to that used in Example 1, electrolysis was performed by changing a phosphorus addition amount as listed in Table 1, and a post-treatment was performed following the same procedures as in Example 1. The specific surfaces area of the obtained electrolytic manganese dioxides are listed in Table 1.
A heat treatment was performed following the same procedures as in Example 1, and a test cell as shown in Fig.
1 was manufactured following the same procedures as in Example 1 by using each electrolytic manganese dioxide. A
discharge test was performed by using this test cell. The obtained relationship between a voltage and a continuous discharge time is shown in Fig. 2.
Examples 4 - 7 By using an apparatus similar to that used in Example 1, electrolysis was performed by adding phosphorous acid, hypophosphorous acid, sodium tripolyphosphate, and potassium - tripolyphosphate in amounts as listed in Table 1, instead of phosphoric acid, and a post-treatment was performed following the same procedures as in Example 1. The specific surfaces area of the obtained electrolytic manganese dioxides are listed in 'l'able 1.
A heat treatment was performed following the same procedures as in Example 1, and a test cell was manufactured followlng the same procedures as in Exalnple 1 by using each electrolytic manganese dioxide. A discharge test was performed by using this test cell. The obtained relationship between a voltage and a continuous discharge time is listed in Fig. 3.
Comparative Example 1 By using an apparatus similar to that used in Example 1, electrolysis was performed following the same procedures as in Example 1 except that no phosphoric acid solution was added, and a post-treatment was performed following the same procedures as in Example 1. The specific surface area of the obtained electrolytic manganese dloxide is listed in lS Table 1.
A heat treatment was performed following the same procedures as in Example 1, and a test cell as shown in Fig.
1 was manufactured following the same procedures as in Example 1 by using this electrolytic manganese dioxide. A
discharge test was performed by using this test cell. The obtained relationship between a voltage and a continuous discharge time is shown in Figs. 2 and 3 so as to be compared with the examples.
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-2CC4i44 As is apparent from Figs. 2 and 3, the test cell obtained by each of Examples 1 to 7 had a much longer continuous discharge time and a higher operation voltage during discharge than those of the test cell obtained by Comparative Example 1. That is, each test cell according to the present invention had very good cell characteristics as a non-hydrous electrolyte cell.
As has been described above, according to the method of the present invention, a phosphoric acid compound or the like is added to the electrolyte during the manufacture of electrolytic manganese dioxide by electrolysis using manganese sulfate and a sulfuric acid solution as the electrolyte. Therefore, the obtained electrolyte manganese dioxide has a larger specific surface area than that of conventional electrolytic manganese dioxide and contains a predetermined amount of phosphorus.
In addition, by using this electrolytic manganese dioxide containing phosphorus as a cathode active material of a lithium primary material, a high discharge voltage and a long discharge time can be achieved.
Since the high discharge voltage and long discharge time can be simultaneously achieved, cell characteristics of the lithium primary cell can be effectively improved.
,,
Lithium Primary Cell, Cathode Active Material Therefor, and Method for Manufacturing Manganese Dioxide for Cathode ~ctive Material BACKGROUND OF THE INVENTION:
Field of the Invention The present invention relates to a lithium primary cell using lithium or a lithium alloy as an anode active material and manganese dioxide as a cathode active material, a cathode active material therefor, and a method for manufacturing manganese dioxide for the cathode active materia 1 .
Description of the Prior Art Manganese dioxide and carbon fluoride are known as typical examples of a cathode active material of a lithium primary cell and are already commercially available.
Of these cathode active materials, manganese dioxide is advantageous since it has a good storage stability and is inexpensive.
A lithium primary cell using manganese dioxide as a cathode active material is currently applied to a camera and the like. As a multi-function of a camera has progressed, a demand has arisen for a lithium primary cell to have a high discharge voltage. A large discharge capacity, i.e., a long discharge time is also demanded for the lithium primary cell. No lithium primary cell, however, which can satisfy both the re~uirements with a good balance, has been proposed.
, ~ - 2 - 2G~474~
SUMMARY OF THE INVENTION:
The present invention has been made in consideration of the above situation and is intended to provide a lithium primary cell which uses manganese dioxide as a cathode active material and achieves both a high discharge voltage and a long discharge time, a cathode active material therefor, and a method for manufacturing manganese dioxide for the cathode active material.
The above object of the present invention is achieved by adding 0.05 to 2.0 parts by weight of phosphorus to 100 parts by weight of manganese dioxide and using the resultant material as a cathode active material of a lithium primary cell.
According to the present invention, manganese dioxide containing phosphorus is used as a cathode active material. When this cathode active material is used for manufacturing a lithium primary cell, both a high discharge voltage and a long discharge time are achieved.
In this case, the content of phosphorus is generally 0.05 to 2.0 parts by weight with respect to 100 parts by weight of manganese dioxide. If the phosphorus content is less than 0.05 parts by weight with respect to 100 parts by weight of manganese dioxide, no sufficient addition effect is obtained in terms of discharge characteristics of a manufactured lithium primary cell. If the phosphorus content exceeds 2.0 parts by weight, discharge characteristics of manganese dioxide of a manufactured lithium primary cell are degraded.
2~,~,4 144 Such manganese dioxide containing phosphorus is manufactured by, e.g., the following method.
That is, manganese dioxide containing phosphorus is manufactured by adding phosphoric acid, phosphorus acid, hypophosphorous acid, or a derivative thereof to an electrolyte during the manufacture of electrolytic manganese dioxide using manganese sulfate and a sulfuric acid solution as the electrolyte.
In this manufacturing method, manganese sulfate and a sulfuric acid solution are used as an electrolyte. Generally, in this electrolyte, a manganese concentration is 20 to S0 g/~, and a sulfuric acid concentration is 30 to 80 g/e. In addition, as electrodes, titanium or the like is used as a cathode, and carbon or the like is used as an anode.
Electrolytic conditions for electrolytic manganese dioxide are generally a bath temperature of 90~ to 100~C and a current density of 50 to 100 A/m2.
In this manufacturing method, phosphoric acid, phosphorous acid, hypophosphorous acid, or a derivative thereof is added to the electrolyte. Examples of the derivative are a sodium salt, a potassium salt, and the like. The phosphoric acid compound or the like is uniformly added together with a manganese sulfate supply solution from an upper portion of an electrolytic cell to between electrode plates.
2~04 744 The concentration of the phosphoric acid compound or the like in the electrolyte is set to be 0.1 to 3.0 g/~, and the electrolytic conditions are adjusted so that phosphorus is contained in an amount falling within the above range in the manufactured electrolytic manganese dioxide.
The electrolytic manganese dioxide manufactured as descr bed above has a large specific surface area of 40 to 150 m /g. If the specific surface area of electrolytic manganese dioxide is smaller than the above value, reaction area with respect to an electrolyte is small and load discharge performance is weak when this electrolytic manganese dioxide is used as a cathode active material to manufacture a lithium primary cell. If the specific surface area of electrolytic manganese dloxide exceeds the above value, a cathode agent becomes bulky. The specific surface area of electrolytic manganese dioxide can be adjusted by arbitrarily selecting the type or content of the phosphoric acid compound.
A lithium primary cell, manufactured under normal conditions by using electrolytic manganese dioxide containing phosphorus as a cathode active material and lithium or a lithium alloy such as lithium-aluminum as an anode, has a higher discharge voltage and a longer discharge time than those of a conventional lithium primary cell.
BRIEF DESCRIPTION OF T~E DRAWINGS:
Fig.-1 is a schematic sectional view for explaining a test cell used in examples and a comparative example; and 2t)C4 ~44 Figs. 2 and 3 are graphs each showing a relationship between a voltage and a continuous discharge time in the examples and comparative example.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT:
The present invention will be described in detail below by way of its examples.
ExamPle 1 A titanium plate as a cathode and a graphite plate as an anode were alternately suspended in an electrolytic cell having a volume of 3~ and equipped with a heating apparatus, and an addition tube was connected to the bottom portion of the electrolytic cell to add an electrolytic supply solution composed of manganese sulfate and a phosphoric acid solution.
The electrolytic supply solution was adjusted so that 0.5 g/e of sulfuric acid were contained in the manganese sulfate solution.
When electrolysis was performed by supplying the supply solution in the electrolytic cell, the composition of the electrolyte was adjusted so that 50 g/~ of manganese and 30 g/e of sulfuric acid were contained. Electrolysis was performed at a bath temperature of 95 il~C and a current density of 100 A/m2 .
After electrolysis was finished, the cathode plate on which electrolytic manganese dioxide was electro-deposited was removed from the cell and subjected to a normal post-treatment, and the specific surface area of the obtained electrolytic manganese dioxide was measured. The measurement results are listed in Table 1.
~ ~ .~ s. ,, 2 0 ~, 4 1 4 4 A heat treatment was performed at 400~C for three hours, 0.135 g of the obtained electrolytic manganese dioxide were measured, and 0.09 g of graphite and 0.06 g of a tetrafluoroethylene resin were mixed therewith. The resultant mixture was pressure-molded at 3 t/cm2 to prepare a cathode mixture. Note that the manganese dioxide, the graphite and the tetrafluoroethylene were predried and mixed.
The prepared cathode mixture was used to form a test cell as shown in Fig. 1, and a 2.5 KQ continuous discharge test was performed at 20~C. All these operations were performed in a dry box in an argon atmosphere. The electrolyte was prepared by dissolving 1 mol/e of lithium perchlorate in a 1:1 solvent mixture of propylenecarbonate and l,2-dimethoxyethane.
A reagent used in this test was dried by a conventional method. In addition, the anode was formed by punching a metal lithium sheet to have the same diameter as that of the cathode mixture.
In the test cell shown in Fig. 1, reference numeral 1 denotes an anode terminal for externally extracting a current; and 2, insulating members made of a Teflon (trademark) resin. The insulating members 2 are threadably engaged with each other to close the cell. Reference numeral 3 denotes an anode platei 4, a crimped metal lithium sheet (anode)i 5, a separator made of a non-woven fabric; 6, a cathode mixture lormed by the above method; and 7, a stainless steel cathode.
A discharge test was performed by using the above test cell. The obtained relationship between a voltage and a continuous discharge time is shown in Fig. 2.
Examples 2 and 3 By using an apparatus similar to that used in Example 1, electrolysis was performed by changing a phosphorus addition amount as listed in Table 1, and a post-treatment was performed following the same procedures as in Example 1. The specific surfaces area of the obtained electrolytic manganese dioxides are listed in Table 1.
A heat treatment was performed following the same procedures as in Example 1, and a test cell as shown in Fig.
1 was manufactured following the same procedures as in Example 1 by using each electrolytic manganese dioxide. A
discharge test was performed by using this test cell. The obtained relationship between a voltage and a continuous discharge time is shown in Fig. 2.
Examples 4 - 7 By using an apparatus similar to that used in Example 1, electrolysis was performed by adding phosphorous acid, hypophosphorous acid, sodium tripolyphosphate, and potassium - tripolyphosphate in amounts as listed in Table 1, instead of phosphoric acid, and a post-treatment was performed following the same procedures as in Example 1. The specific surfaces area of the obtained electrolytic manganese dioxides are listed in 'l'able 1.
A heat treatment was performed following the same procedures as in Example 1, and a test cell was manufactured followlng the same procedures as in Exalnple 1 by using each electrolytic manganese dioxide. A discharge test was performed by using this test cell. The obtained relationship between a voltage and a continuous discharge time is listed in Fig. 3.
Comparative Example 1 By using an apparatus similar to that used in Example 1, electrolysis was performed following the same procedures as in Example 1 except that no phosphoric acid solution was added, and a post-treatment was performed following the same procedures as in Example 1. The specific surface area of the obtained electrolytic manganese dloxide is listed in lS Table 1.
A heat treatment was performed following the same procedures as in Example 1, and a test cell as shown in Fig.
1 was manufactured following the same procedures as in Example 1 by using this electrolytic manganese dioxide. A
discharge test was performed by using this test cell. The obtained relationship between a voltage and a continuous discharge time is shown in Figs. 2 and 3 so as to be compared with the examples.
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-2CC4i44 As is apparent from Figs. 2 and 3, the test cell obtained by each of Examples 1 to 7 had a much longer continuous discharge time and a higher operation voltage during discharge than those of the test cell obtained by Comparative Example 1. That is, each test cell according to the present invention had very good cell characteristics as a non-hydrous electrolyte cell.
As has been described above, according to the method of the present invention, a phosphoric acid compound or the like is added to the electrolyte during the manufacture of electrolytic manganese dioxide by electrolysis using manganese sulfate and a sulfuric acid solution as the electrolyte. Therefore, the obtained electrolyte manganese dioxide has a larger specific surface area than that of conventional electrolytic manganese dioxide and contains a predetermined amount of phosphorus.
In addition, by using this electrolytic manganese dioxide containing phosphorus as a cathode active material of a lithium primary material, a high discharge voltage and a long discharge time can be achieved.
Since the high discharge voltage and long discharge time can be simultaneously achieved, cell characteristics of the lithium primary cell can be effectively improved.
,,
Claims (7)
1. A method of manufacturing manganese dioxide for a lithium primary cell containing 0.05 to 2.0 parts by weight of phosphorus per 100 parts by weight of manganese dioxide which consists of introducing a manganese sulfate solution and sulfuric acid as an electrolyte into an electrolytic cell, adding to said electrolyte at least one member selected from the group consisting of phosphoric acid, phosphorus acid hypophosphorus acid and sodium or potassium salts thereof and carrying out the electrolysis at a bath temperature of 90° to 100°C whereby manganese dioxide which contains phosphorus is electrodeposited on the cathode.
2. The method according to claim 1 wherein said at least one member added to said electrolyte is phosphoric acid.
3. The method according to claim 1 wherein said electrolysis is carried out at a current density of 50 to 100 A/m2.
4. The method according to claim 2 wherein said electrolysis is carried out at a current density of 50 to 100 A/m2.
5. The method according to claim 1 wherein the manganese concentration in said electrolyte is 20 to 50 g/l.
6. The method according to claim 1 wherein the sulfuric acid concentration in said electrolyte is 30 to 80 g/l.
7. A lithium primary cell which comprises lithium or a lithium alloy as an anode active material and manganese dioxide as a cathode active material, characterized in that said manganese dioxide contains 0.05 - 2 parts by weight of phosphorus per 100 parts by weight of manganese dioxide thereby enabling the lithium primary cell to exhibit higher discharge voltage and longer discharge time than one wherein the manganese dioxide is devoid of a phosphorus compound.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63309396A JPH061698B2 (en) | 1988-12-07 | 1988-12-07 | Lithium primary battery, anode active material thereof, and method for producing manganese dioxide used in the anode active material |
| JP63-309396 | 1988-12-07 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2004744A1 CA2004744A1 (en) | 1990-06-07 |
| CA2004744C true CA2004744C (en) | 1998-02-17 |
Family
ID=17992511
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002004744A Expired - Fee Related CA2004744C (en) | 1988-12-07 | 1989-12-06 | Lithium primary cell, cathode active material therefor, and method for manufacturing manganese dioxide for cathode active material |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US5156933A (en) |
| EP (1) | EP0373791B1 (en) |
| JP (1) | JPH061698B2 (en) |
| AU (1) | AU4567989A (en) |
| CA (1) | CA2004744C (en) |
| DE (1) | DE68914960T2 (en) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5312457A (en) * | 1992-07-01 | 1994-05-17 | Kerr-Mcgee Chemical Corporation | Use of hydroquinone to precondition manganese dioxide for use in rechargeable electrochemical cells |
| US5277890A (en) * | 1992-09-28 | 1994-01-11 | Duracell Inc. | Process for producing manganese dioxide |
| JP3342769B2 (en) * | 1994-03-31 | 2002-11-11 | 三井金属鉱業株式会社 | Manganese dioxide for lithium primary battery and method for producing the same |
| JP2001236957A (en) | 2000-02-25 | 2001-08-31 | Mitsui Mining & Smelting Co Ltd | Manganese dioxide for lithium primary battery and method for producing the same |
| ATE290721T1 (en) * | 2000-06-01 | 2005-03-15 | Eveready Battery Inc | DOPED MANGANESE DIOXIDES |
| US20050048366A1 (en) | 2003-08-27 | 2005-03-03 | Bowden William L. | Cathode material and method of manufacturing |
| US8003254B2 (en) | 2004-01-22 | 2011-08-23 | The Gillette Company | Battery cathodes |
| US20050164085A1 (en) * | 2004-01-22 | 2005-07-28 | Bofinger Todd E. | Cathode material for lithium battery |
| US8137842B2 (en) | 2004-01-22 | 2012-03-20 | The Gillette Company | Battery cathodes |
| US20220376270A1 (en) * | 2019-11-05 | 2022-11-24 | Maxell, Ltd. | Lithium primary battery pack and gas meter |
| CN115579467A (en) * | 2022-09-20 | 2023-01-06 | 东莞理工学院 | A kind of synthesis method of phosphorus-doped manganese dioxide and its application in zinc-ion battery |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4069116A (en) * | 1976-05-25 | 1978-01-17 | Levan Nikolaevich Dzhaparidze | Electrochemical process for producing manganese dioxide |
| JPS5755065A (en) * | 1980-09-19 | 1982-04-01 | Sanyo Electric Co Ltd | Positive electrode of non-aqueous electrolyte cell |
| US4465747A (en) * | 1983-06-29 | 1984-08-14 | Union Carbide Corporation | Alkali metal or alkaline earth metal compound additive for manganese dioxide-containing nonaqueous cells |
| US4478921A (en) * | 1983-09-28 | 1984-10-23 | Union Carbide Corporation | Manganese carbonate additive for manganese dioxide-containing nonaqueous cells |
| JPH01200557A (en) * | 1987-10-13 | 1989-08-11 | Bridgestone Corp | Nonaqueous electrolytic battery |
| JPH02213487A (en) * | 1988-12-26 | 1990-08-24 | Japan Metals & Chem Co Ltd | Manufacture of electrolytic manganese dioxide |
| JP3054018B2 (en) * | 1993-12-28 | 2000-06-19 | イビデン株式会社 | Manufacturing method of printed wiring board |
-
1988
- 1988-12-07 JP JP63309396A patent/JPH061698B2/en not_active Expired - Fee Related
-
1989
- 1989-11-29 DE DE68914960T patent/DE68914960T2/en not_active Expired - Fee Related
- 1989-11-29 AU AU45679/89A patent/AU4567989A/en not_active Abandoned
- 1989-11-29 EP EP89312439A patent/EP0373791B1/en not_active Expired - Lifetime
- 1989-12-06 CA CA002004744A patent/CA2004744C/en not_active Expired - Fee Related
-
1991
- 1991-04-11 US US07/684,169 patent/US5156933A/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| CA2004744A1 (en) | 1990-06-07 |
| JPH02155166A (en) | 1990-06-14 |
| EP0373791A1 (en) | 1990-06-20 |
| DE68914960D1 (en) | 1994-06-01 |
| AU4567989A (en) | 1990-06-14 |
| DE68914960T2 (en) | 1994-08-11 |
| JPH061698B2 (en) | 1994-01-05 |
| US5156933A (en) | 1992-10-20 |
| EP0373791B1 (en) | 1994-04-27 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request | ||
| MKLA | Lapsed | ||
| MKLA | Lapsed |
Effective date: 20081208 |