CN104746108A - Method for preparing battery anode material by utilizing graphene enhanced electrolytic manganese anode slime - Google Patents
Method for preparing battery anode material by utilizing graphene enhanced electrolytic manganese anode slime Download PDFInfo
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- CN104746108A CN104746108A CN201510195938.8A CN201510195938A CN104746108A CN 104746108 A CN104746108 A CN 104746108A CN 201510195938 A CN201510195938 A CN 201510195938A CN 104746108 A CN104746108 A CN 104746108A
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Abstract
The invention relates to a method for preparing a battery anode material by utilizing graphene enhanced electrolytic manganese anode slime. The method comprises the following steps: (1) drying the electrolytic manganese anode slime under the condition of 30 to 100 DEG C; (2) crushing and filtering the dried electrolytic manganese anode slime to obtain powder with particle size less than or equal to 0.150mm; (3) burning the powder under the condition of 100 to 400 DEG C; (4) uniformly mixing the electrolytic manganese anode slime after treated in the step (3) and graphene to obtain the battery anode material, wherein the mass percent of the graphene is 1.5 to 4 percent. Compared with the prior art, on the aspect of reducing the pollution and recycling the electrolytic manganese anode mud, the entire operating process is simpler, and the continuous discharging time after the battery is fully charged is longer.
Description
Technical field
The present invention relates to the method for producing battery raw material utilizing electrolytic manganese anode mud.
Background technology
Electrolytic manganese anode mud produces in the process of manganese by electrolytic process the by product be deposited in anolyte compartment, owing to still containing the very important manganese element (certainly also having other impurity) of content in electrolytic manganese anode mud, so, if store away as waste heap or sell at a bargain after they are removed, not only can cause the pollution to environment, also result in the waste of promoter manganese simultaneously.Therefore, for improving the utility value of Manganese anode slime, people are just exploring the various methods of recycling electrolytic manganese anode mud always.Notification number is CN101717860B, name is called the patent of " method and goods thereof that a kind of electrolytic manganese anode mud prepares battery raw material ", is exactly one of this kind of exploration achievement.The step of the prior art employing method is, 1. electrolytic manganese anode mud is dried to its water ratio not higher than 3% degree, then with H
2sO
4solution fully mixes, fully stir; 2. then carry out solid-liquid separation and wash decorating film with clear water, in washings till sulfate radical-free ion; 3. the decorating film after washing is dried, until the water ratio of this oven dry decorating film is 1 ~ 3%; 4. in oven dry decorating film, add ionic liquid and mix, to obtain raw material---the i.e. anode raw material containing activated manganese dioxide.In recycling electrolytic manganese anode mud, the prior art achieves good technique effect really, but the prior art but exists the continuous discharge time after being full of electricity, and length, whole operating process are also about complicated deficiency a bit not enough.
Summary of the invention
The object of this invention is to provide a kind of whole operating process more simple, be full of electricity after the continuous discharge time longer method preparing cell positive material with the electrolytic manganese anode mud that Graphene strengthens.
For realizing described object, the electrolytic manganese anode mud providing a kind of like this Graphene to strengthen prepares the method for cell positive material, and aspect same as the prior art is, first the method comprises will make the step (1) of drying treatment by electrolytic manganese anode mud.Its improvements are, the drying temperature in described step (1) is 30 ~ 100 DEG C; Then following steps are carried out:
(2) dried electrolytic manganese anode mud is pulverized, sieved, obtain pulverous electrolytic manganese anode mud that particle diameter is not more than 0.150mm;
(3) electrolytic manganese anode mud after step (2) being processed is placed in calcination under 100 ~ 400 DEG C of conditions, and the time is 1 ~ 5 hour;
(4) electrolytic manganese anode mud after step (3) being processed mixes with graphene uniform, obtains cell positive material; In this cell positive material, the mass percent of Graphene is 1.5 ~ 4%.
As can be seen from scheme, present invention omits in prior art and electrolytic manganese anode mud is mixed with sulfuric acid, then eliminate the step of sulfate ion again.Although these two steps eliminated can offset with pulverizing of the present invention and calcination substantially, the present invention still eliminates after all must the process preparing a kind of raw material more.
Carrying out calcination to pulverous electrolytic manganese anode mud in step (3), remove the impurity be contained in electrolytic manganese anode mud in fact exactly by calcination, is also simultaneously by wherein can not electrolysis and be not all converted into the process of Manganse Dioxide by the manganese of electrolysis.Checking shows, the Manganse Dioxide that the Manganse Dioxide transformed by calcination and electrolysis are produced, through calcination, can make these Manganse Dioxide have better chemical property better.The Graphene of mixing in step (4), inherently have unique chemical property, at present, the product of the existing conductivity type Graphene produced by special process, has had again graphene battery to be developed out.Just, conductivity type Graphene is almost be made up of absolutely Graphene; In graphene battery, no matter be that consumption all can only based on Graphene or act on.And in the present invention, only use a small amount of and Graphene that do not need special process to process.Checking shows, in the cell positive material of step (4) gained, if the mass percent of Graphene is more than 4%, the continuous discharge time after electricity that is full of can shorten greatly; When Graphene mass percent lower than 1.5%, be full of the continuous discharge time after electricity just not how many than the length of the electrolytic manganese anode mud after step (3) calcination process again.Therefore, can assert like this, in the ratio range that step (4) is determined, the Manganse Dioxide in electrolytic manganese anode mud and Graphene have the effect of mutually working in coordination with, mutually promoting, and then can obtain the cell positive material of applicable service requirements.Checking shows equally, and the effect of thisly mutually to work in coordination with, mutually promoting is also larger.Compared with prior art, the present invention not only whole operating process is more simple, and key is also that the continuous discharge time after being full of electricity is longer.
Below in conjunction with embodiment, the present invention is further illustrated.
Embodiment
Prepare the method for cell positive material with the electrolytic manganese anode mud that Graphene strengthens, first the method comprises will make the step (1) of drying treatment by electrolytic manganese anode mud.In the present invention, the drying temperature in described step (1) is 30 ~ 100 DEG C; Then following steps are carried out:
(2) dried electrolytic manganese anode mud is pulverized, sieved, obtain pulverous electrolytic manganese anode mud that particle diameter is not more than 0.150mm;
(3) electrolytic manganese anode mud after step (2) being processed is placed in calcination under 100 ~ 400 DEG C of conditions, and the time is 1 ~ 5 hour;
(4) electrolytic manganese anode mud after step (3) being processed mixes with graphene uniform, obtains cell positive material; In this cell positive material, the mass percent of Graphene is 1.5 ~ 4%.
The comparative tests that the present invention have passed through in laboratory is verified, during checking, electrolytic manganese anode mud used is all from the same electrolytic manganese factory in Xiushan, Chongqing county.
Comparative example adopts a kind of method described in " electrolytic manganese anode mud prepares method and the goods thereof of battery raw material " of CN101717860B, except wherein " step 3. rear institute gets oven dry decorating film quality " has only got except 20g when contrasting, all the other components are identical with " example 6 " of CN101717860B with the selection of proportioning.
Identical with described in above-mentioned embodiment of proof procedure of the present invention, the electrolytic manganese anode mud after step (3) process, each checking example all unification gets 20g, to ensure there is comparability with prior art.
After above-mentioned experiment terminates, all detect by identical battery performance detection method, checking and detected result are shown in that proof list (for proof list is simple, clear, all do not record by all fixed numbers mentioned above; Effect is recorded and is compared, and only listing can " specific storage " and " being full of the continuous discharge time after electricity " of reaction cell positive electrode material characteristic and performance).
Proof list:
As can be seen from above-mentioned checking example, compared with prior art, take electrolytic manganese anode mud as the cell positive material of main raw material prepared by the inventive method, and its specific storage and these two the leading indicator aspects of continuous discharge time after being full of electricity, had and significantly improved.Especially, when the Graphene mass percent be documented in this cell positive material of checking example 2 is 2%, increase rate is larger.
Claims (1)
1. prepare the method for cell positive material with the electrolytic manganese anode mud that Graphene strengthens, first the method comprises will make the step (1) of drying treatment by electrolytic manganese anode mud, it is characterized in that, the drying temperature in described step (1) is 30 ~ 100 DEG C; Then following steps are carried out:
(2) dried electrolytic manganese anode mud is pulverized, sieved, obtain pulverous electrolytic manganese anode mud that particle diameter is not more than 0.150mm;
(3) electrolytic manganese anode mud after step (2) being processed is placed in calcination under 100 ~ 400 DEG C of conditions, and the time is 1 ~ 5 hour;
(4) electrolytic manganese anode mud after step (3) being processed mixes with graphene uniform, obtains cell positive material; In this cell positive material, the mass percent of Graphene is 1.5 ~ 4%.
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| CN201510195938.8A CN104746108A (en) | 2015-04-23 | 2015-04-23 | Method for preparing battery anode material by utilizing graphene enhanced electrolytic manganese anode slime |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109824121A (en) * | 2019-03-26 | 2019-05-31 | 湖南柿竹园有色金属有限责任公司 | A kind of Wastewater by Electric catalyticing anode and its preparation method and application |
| CN113234941A (en) * | 2021-05-18 | 2021-08-10 | 西南科技大学 | High-value utilization method of electrolytic manganese anode slime |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102339994A (en) * | 2010-07-23 | 2012-02-01 | 中国科学院宁波材料技术与工程研究所 | Transition metal oxide/ graphene nanometer composite electrode material used for lithium battery and preparation method thereof |
| CN102876897A (en) * | 2012-09-26 | 2013-01-16 | 中信锦州金属股份有限公司 | Recovery and purification method of manganese dioxide in electrolytic manganese anode mud |
-
2015
- 2015-04-23 CN CN201510195938.8A patent/CN104746108A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102339994A (en) * | 2010-07-23 | 2012-02-01 | 中国科学院宁波材料技术与工程研究所 | Transition metal oxide/ graphene nanometer composite electrode material used for lithium battery and preparation method thereof |
| CN102876897A (en) * | 2012-09-26 | 2013-01-16 | 中信锦州金属股份有限公司 | Recovery and purification method of manganese dioxide in electrolytic manganese anode mud |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109824121A (en) * | 2019-03-26 | 2019-05-31 | 湖南柿竹园有色金属有限责任公司 | A kind of Wastewater by Electric catalyticing anode and its preparation method and application |
| CN109824121B (en) * | 2019-03-26 | 2022-04-22 | 湖南柿竹园有色金属有限责任公司 | Wastewater electrocatalytic anode and preparation method and application thereof |
| CN113234941A (en) * | 2021-05-18 | 2021-08-10 | 西南科技大学 | High-value utilization method of electrolytic manganese anode slime |
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