CN1035118C - Preparation of carbon-electrolytic manganese dioxide composite - Google Patents
Preparation of carbon-electrolytic manganese dioxide composite Download PDFInfo
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- CN1035118C CN1035118C CN94116718A CN94116718A CN1035118C CN 1035118 C CN1035118 C CN 1035118C CN 94116718 A CN94116718 A CN 94116718A CN 94116718 A CN94116718 A CN 94116718A CN 1035118 C CN1035118 C CN 1035118C
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- Prior art keywords
- manganese dioxide
- composite material
- dioxide composite
- carbon
- acid
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- 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.)
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- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 239000002131 composite material Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title abstract description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 101
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 35
- 239000002253 acid Substances 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 33
- 239000003792 electrolyte Substances 0.000 claims abstract description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 42
- 238000002156 mixing Methods 0.000 claims description 33
- 239000006230 acetylene black Substances 0.000 claims description 27
- 239000000843 powder Substances 0.000 claims description 26
- 239000008151 electrolyte solution Substances 0.000 claims description 16
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 13
- 229910017604 nitric acid Inorganic materials 0.000 claims description 13
- 238000005868 electrolysis reaction Methods 0.000 claims description 11
- 239000000243 solution Substances 0.000 claims description 11
- 206010013786 Dry skin Diseases 0.000 claims description 10
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- 229910002804 graphite Inorganic materials 0.000 claims description 10
- 239000010439 graphite Substances 0.000 claims description 10
- KNLQKHUBPCXPQD-UHFFFAOYSA-N manganese;sulfuric acid Chemical compound [Mn].OS(O)(=O)=O KNLQKHUBPCXPQD-UHFFFAOYSA-N 0.000 claims description 10
- 239000010936 titanium Substances 0.000 claims description 10
- 229910052719 titanium Inorganic materials 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 7
- 229910001069 Ti alloy Inorganic materials 0.000 claims description 4
- 239000000376 reactant Substances 0.000 claims description 2
- 230000002349 favourable effect Effects 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
-
- 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)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The present invention relates to a method for preparing carbon electrolytic manganese dioxide composite material by an electrolytic method, which is a preparation method of the carbon electrolytic manganese dioxide and is realized by the following measures: firstly, carbon powder is treated by mixed acid, and then, the treated carbon powder is placed in manganese dioxide electrolyte to be electrolyzed, and the carbon electrolytic manganese dioxide is obtained on an anode. Compared with the common electrolytic manganese dioxide, the carbon electrolytic manganese dioxide prepared by the present invention has the advantages of high electric conductivity and reduced hardness, is favorable for processing and is capable of obviously improving the discharge capacity when used in batteries.
Description
The present invention relates to utilize electrolytic process to prepare the method for carbon element-manganese dioxide composite material, be the method that a kind of electrolytic process prepares carbon element-manganese dioxide composite material, and be used for battery with the carbon element-manganese dioxide composite material of method for preparing and can improve loading capacity.
Usually the electrolytic manganese dioxide of producing is the γ type, and its hardness is big, and is industrial with in the ball mill ground process, more introducing iron contamination, thus influence the battery storage performance.For overcoming these shortcomings, the electrolytic manganese dioxide for preparing behind the suspension carbon element in electrolytic solution can improve loading capacity, as: the Japanese Patent spy opens clear 61-47911 and discloses a kind of carbon element-manganese dioxide composite material preparation method, and this method at first is to make it to become hydroaropic substance with oleum processing acetylene black to be dispersed in the electrolytic solution.But when handling carbon element, exist contaminative big, shortcomings such as operation inconvenience with aforesaid method.
The objective of the invention is to propose the method that a kind of electrolytic process with mixing acid processing carbon powder after carry out more better than prior art prepares carbon element-manganese dioxide composite material.
Be used for battery with the carbon element-manganese dioxide composite material of method for preparing and can improve loading capacity.
The objective of the invention is to realize by following measure: at first handle carbon powder with mixing acid, the carbon powder after will handling is then put into the electrolytic solution of being made up of manganous sulfate and sulfuric acid and is carried out electrolysis, just obtains carbon element-manganese dioxide composite material on anode.
Wherein, the process of handling carbon powder with mixing acid is: at first handled carbon powder 1 to 2 hour with mixing acid under 70 ℃ to 90 ℃, to be cooled then to room temperature, product is filtered out, and after washing with water, just obtain reactant again after 70 ℃ to 90 ℃ following dryings, the volume proportion of mixing acid and carbon powder is 2: 1 to 3: 1; Electrolytic solution be every liter contain 0.50 mole to 1.20 mol sulfuric acid manganese and 0.20 mole to 0.50 mol sulfuric acid solution and add the carbon powder that 0.5 gram was handled with mixing acid to 4.0 grams; Mixing acid is the mixing acid of sulfuric acid and nitric acid, and the volume proportion of its sulfuric acid and nitric acid is 1: 4 to 20: 1; Carbon powder is acetylene black powder or Graphite Powder 99; Anodic current density is 0.7 to 2.0A/dm
2Electrolyte temperature is 88 ℃ to 98 ℃; Anode adopts titanium electrode or titanium alloy electrode or sandblast titanium electrode; Negative electrode adopts Graphite Electrodes; This carbon element-manganese dioxide composite material is used for battery can improve its loading capacity.
Below in conjunction with embodiment the present invention is done further to discuss in detail: at first handle carbon powder with the mixing acid of sulfuric acid and nitric acid, carbon powder after will handling is then put into the electrolytic solution of being made up of manganous sulfate and sulfuric acid and is carried out electrolysis, just obtains carbon element-manganese dioxide composite material on anode;
Wherein, electrolytic solution is manganous sulfate and vitriolic solution and has added the carbon powder of handling with mixing acid; If manganous sulfate concentration is when too low, output is less, and manganous sulfate concentration is when too high, and specific conductivity is low excessively, and energy consumption is higher; If when sulfuric acid concentration is too high (as 2 mol), Manganse Dioxide content significantly reduces; When if sulfuric acid concentration is too low, though the crystal formation of the Manganse Dioxide of product, contains a spot of α and β type based on the γ type; When acidity during, then there is a large amount of α types to exist up to 2 mol; Is good by the control to temperature, concentration, current density to help making required carbon element-manganese dioxide composite material; Below be specific embodiment:
Embodiment 1, be that 1: 4 mixing acid and acetylene black powder mixes at first with the sulfuric acid and the volume ratio of nitric acid, the volume ratio of its mixing acid and acetylene black powder is 2: 1, reaction is after 2 hours under temperature is 70 ℃, to be cooled again to room temperature, product is filtered out, and after washing with water, must arrive 70 ℃ of following dryings again and handle the acetylene black powder; Containing rub vitriolic solution and add 0.5 gram and handle the acetylene black powder and just obtain electrolytic solution of 0.50 mol sulfuric acid manganese and 0.20 at every liter then, is 0.7A/dm in anodic current density
2, electrolyte temperature is 88 ℃ and carries out electrolysis, is to obtain carbon element-manganese dioxide composite material on the titanium electrode (negative electrode is a Graphite Electrodes) at anode just.
Embodiment 2, be that 20: 1 mixing acid and acetylene black powder mixes at first with the sulfuric acid and the volume ratio of nitric acid, the volume ratio of its mixing acid and acetylene black powder is 3: 1, reaction is after 1 hour under temperature is 90 ℃, to be cooled again to room temperature, product is filtered out, and after washing with water, must arrive 73 ℃ of following dryings again and handle the acetylene black powder; Containing rub vitriolic solution and add 4.0 grams and handle the acetylene black powder and just obtain electrolytic solution of 1.20 mol sulfuric acid manganese and 0.50 at every liter then, is 2.0A/dm in anodic current density
2, electrolyte temperature is 98 ℃ and carries out electrolysis, is to obtain carbon element-manganese dioxide composite material on the titanium alloy electrode (negative electrode is a Graphite Electrodes) at anode just.
Embodiment 3, be that 1: 2 mixing acid and acetylene black powder mixes at first with the sulfuric acid and the volume ratio of nitric acid, the volume ratio of its mixing acid and acetylene black powder is 2: 1, reaction is after 2 hours under temperature is 75 ℃, to be cooled again to room temperature, product is filtered out, and after washing with water, must arrive 75 ℃ of following dryings again and handle the acetylene black powder; Containing rub vitriolic solution and add 1.0 grams and handle the acetylene black powder and just obtain electrolytic solution of 0.80 mol sulfuric acid manganese and 0.30 at every liter then, is 0.9A/dm in anodic current density
2, electrolyte temperature is 90 ℃ and carries out electrolysis, is to obtain carbon element-manganese dioxide composite material on the sandblast titanium electrode (negative electrode is a Graphite Electrodes) at anode just.
Embodiment 4, be that 4: 1 mixing acid and acetylene black powder mixes at first with the sulfuric acid and the volume ratio of nitric acid, the volume ratio of its mixing acid and acetylene black powder is 3: 1, reaction is after 2 hours under temperature is 80 ℃, to be cooled again to room temperature, product is filtered out, and after washing with water, must arrive 78 ℃ of following dryings again and handle the acetylene black powder; Containing rub vitriolic solution and add 1.5 grams and handle the acetylene black powder and just obtain electrolytic solution of 1.00 mol sulfuric acid manganese and 0.40 at every liter then, is 1.2A/dm in anodic current density
2, electrolyte temperature is 92 ℃ and carries out electrolysis, is to obtain carbon element-manganese dioxide composite material on the titanium electrode (negative electrode is a Graphite Electrodes) at anode just.
Embodiment 5, be that 18: 1 mixing acid and Graphite Powder 99 mixes at first with the sulfuric acid and the volume ratio of nitric acid, the volume ratio of its mixing acid and Graphite Powder 99 is 2: 1, reaction is after 1 hour under temperature is 85 ℃, to be cooled again to room temperature, product is filtered out, and after washing with water, must arrive 82 ℃ of following dryings again and handle Graphite Powder 99; Containing rub vitriolic solution and add 2.0 grams and handle Graphite Powder 99s and just obtain electrolytic solution of 1.20 mol sulfuric acid manganese and 0.20 at every liter then, is 1.4A/dm in anodic current density
2, electrolyte temperature is 94 ℃ and carries out electrolysis, is to obtain carbon element-manganese dioxide composite material on the titanium electrode (negative electrode is a Graphite Electrodes) at anode just.
Embodiment 6, be that 12: 1 mixing acid and acetylene black powder mixes at first with the sulfuric acid and the volume ratio of nitric acid, the volume ratio of its mixing acid and acetylene black powder is 3: 1, reaction is after 1 hour under temperature is 90 ℃, to be cooled again to room temperature, product is filtered out, and after washing with water, must arrive 86 ℃ of following dryings again and handle the acetylene black powder; Containing rub vitriolic solution and add 2.5 grams and handle the acetylene black powder and just obtain electrolytic solution of 1.10 mol sulfuric acid manganese and 0.25 at every liter then, is 1.6A/dm in anodic current density
2, electrolyte temperature is 96 ℃ and carries out electrolysis, is to obtain carbon element-manganese dioxide composite material on the titanium alloy electrode (negative electrode is a Graphite Electrodes) at anode just.
Embodiment 7, be that 20: 1 mixing acid and Graphite Powder 99 mixes at first with the sulfuric acid and the volume ratio of nitric acid, the volume ratio of its mixing acid and Graphite Powder 99 is 2: 1, reaction is after 2 hours under temperature is 70 ℃, to be cooled again to room temperature, product is filtered out, and after washing with water, must arrive 88 ℃ of following dryings again and handle Graphite Powder 99; Containing rub vitriolic solution and add 3.0 grams and handle Graphite Powder 99s and just obtain electrolytic solution of 0.90 mol sulfuric acid manganese and 0.35 at every liter then, is 1.8A/dm in anodic current density
2, electrolyte temperature is 98 ℃ and carries out electrolysis, is to obtain carbon element-manganese dioxide composite material on the sandblast titanium electrode (negative electrode is a Graphite Electrodes) at anode just.
Embodiment 8, be that 8: 1 mixing acid and acetylene black powder mixes at first with the sulfuric acid and the volume ratio of nitric acid, the volume ratio of its mixing acid and acetylene black powder is 3: 1, reaction is after 2 hours under temperature is 72 ℃, to be cooled again to room temperature, product is filtered out, and after washing with water, must arrive 90 ℃ of following dryings again and handle the acetylene black powder; Containing rub vitriolic solution and add 3.5 grams and handle the acetylene black powder and just obtain electrolytic solution of 0.70 mol sulfuric acid manganese and 0.45 at every liter then, is 2.0A/dm in anodic current density
2, electrolyte temperature is 95 ℃ and carries out electrolysis, is to obtain carbon element-manganese dioxide composite material on the titanium electrode (negative electrode is a Graphite Electrodes) at anode just.
Adopt the carbon element-manganese dioxide composite material of the present invention's preparation to compare with general electrolytic manganese dioxide: its electric conductivity height, hardness reduces and helps processing, is used for battery and can obviously improves loading capacity.
Below for the battery made with international sample No. 1 (being I.C.NO.1) and embodiment 1 to 8 in+0.3 volt to-0.4 volt interval with+0.3 volt to-1.0 volts interval constant-current discharge result:
| Sample | Take-off potential (volt) | + 0.3 to-0.4 volt of interval constant-current discharge (minute) | + 0.3 to-1.0 volt of interval constant-current discharge (minute) |
| No. 1, sample | +0.221 | 174 | 294 |
| Embodiment 1 | +0.180 | 210 | 335 |
| Embodiment 2 | +0.160 | 200 | 308 |
| Embodiment 3 | +0.209 | 205 | 311 |
| Embodiment 4 | +0.163 | 202 | 317 |
| Embodiment 5 | +0.167 | 195 | 291 |
| Embodiment 6 | +0.162 | 198 | 321 |
| Embodiment 7 | +0.169 | 201 | 315 |
| Embodiment 8 | +0.175 | 199 | 320 |
Claims (8)
1. an electrolytic process prepares the method for carbon element-manganese dioxide composite material, it is characterized in that: at first handle carbon powder with mixing acid, carbon powder after will handling is then put into the electrolytic solution of being made up of manganous sulfate and sulfuric acid and is carried out electrolysis, just on anode, obtain carbon element-manganese dioxide composite material, wherein, mixing acid is the mixing acid of sulfuric acid and nitric acid, and the volume proportion of its sulfuric acid and nitric acid is 1: 4 to 20: 1.
2. electrolytic process according to claim 1 prepares the method for carbon element-manganese dioxide composite material, it is characterized in that the process of handling carbon powder with mixing acid is: at first under 70 ℃ to 90 ℃, handled carbon powder 1 to 2 hour with mixing acid, to be cooled then to room temperature, product is filtered out, and after washing with water, after 70 ℃ to 90 ℃ following dryings, just obtain reactant again; The volume proportion of mixing acid and carbon powder is 2: 1 to 3: 1.
3. electrolytic process according to claim 1 prepares the method for carbon element-manganese dioxide composite material, it is characterized in that the electrolytic solution of forming by manganous sulfate and sulfuric acid be every liter contain 0.50 mole to 1.20 mol sulfuric acid manganese and 0.20 mole to 0.50 mol sulfuric acid solution and add the carbon powder that 0.5 gram was handled with mixing acid to 4.0 grams.
4. prepare the method for carbon element-manganese dioxide composite material according to claim 1 or 2 or 3 described electrolytic process, it is characterized in that carbon powder is acetylene black powder or Graphite Powder 99.
5. electrolytic process according to claim 1 prepares the method for carbon element-manganese dioxide composite material, it is characterized in that anodic current density is 0.7 to 2.0A/dm
2
6. electrolytic process according to claim 1 prepares the method for carbon element-manganese dioxide composite material, it is characterized in that electrolyte temperature is 88 ℃ to 98 ℃.
7. electrolytic process according to claim 1 prepares the method for carbon element-manganese dioxide composite material, it is characterized in that anode adopts titanium electrode or titanium alloy electrode or sandblast titanium electrode.
8. electrolytic process according to claim 1 prepares the method for carbon element-manganese dioxide composite material, it is characterized in that negative electrode adopts Graphite Electrodes.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94116718A CN1035118C (en) | 1994-10-01 | 1994-10-01 | Preparation of carbon-electrolytic manganese dioxide composite |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94116718A CN1035118C (en) | 1994-10-01 | 1994-10-01 | Preparation of carbon-electrolytic manganese dioxide composite |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1101385A CN1101385A (en) | 1995-04-12 |
| CN1035118C true CN1035118C (en) | 1997-06-11 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN94116718A Expired - Fee Related CN1035118C (en) | 1994-10-01 | 1994-10-01 | Preparation of carbon-electrolytic manganese dioxide composite |
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| Country | Link |
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| CN (1) | CN1035118C (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116005175A (en) * | 2022-12-20 | 2023-04-25 | 安徽诚越电子科技有限公司 | Superelectrolytic manganese dioxide and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02175888A (en) * | 1988-12-28 | 1990-07-09 | Mitsui Mining & Smelting Co Ltd | Production of electrolytic manganese dioxide |
| JPH02213487A (en) * | 1988-12-26 | 1990-08-24 | Japan Metals & Chem Co Ltd | Manufacture of electrolytic manganese dioxide |
| CN1047708A (en) * | 1988-05-29 | 1990-12-12 | 福建师范大学 | Production process of fibrous electrolytic manganese dioxide, corresponding device and special electrode |
| JP4110485B2 (en) * | 1996-03-27 | 2008-07-02 | ウステル・テヒノロジーズ・アクチエンゲゼルシヤフト | Method and apparatus for monitoring yarn quality |
-
1994
- 1994-10-01 CN CN94116718A patent/CN1035118C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1047708A (en) * | 1988-05-29 | 1990-12-12 | 福建师范大学 | Production process of fibrous electrolytic manganese dioxide, corresponding device and special electrode |
| JPH02213487A (en) * | 1988-12-26 | 1990-08-24 | Japan Metals & Chem Co Ltd | Manufacture of electrolytic manganese dioxide |
| JPH02175888A (en) * | 1988-12-28 | 1990-07-09 | Mitsui Mining & Smelting Co Ltd | Production of electrolytic manganese dioxide |
| JP4110485B2 (en) * | 1996-03-27 | 2008-07-02 | ウステル・テヒノロジーズ・アクチエンゲゼルシヤフト | Method and apparatus for monitoring yarn quality |
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| Publication number | Publication date |
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| CN1101385A (en) | 1995-04-12 |
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