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
- Publication number
- 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
- Authority
- CN
- China
- Prior art keywords
- electrolytic manganese
- anode slime
- manganese anode
- graphene
- positive electrode
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 48
- 239000011572 manganese Substances 0.000 title claims abstract description 48
- 238000000034 method Methods 0.000 title claims abstract description 27
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 25
- 239000010405 anode material Substances 0.000 title description 4
- 239000007774 positive electrode material Substances 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 7
- 238000007873 sieving Methods 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 239000008187 granular material Substances 0.000 abstract 1
- 238000012795 verification Methods 0.000 description 12
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 10
- 239000002994 raw material Substances 0.000 description 7
- 239000007787 solid Substances 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Battery Electrode And Active Subsutance (AREA)
- Primary Cells (AREA)
Abstract
用石墨烯增强的电解锰阳极泥制备电池正极材料的方法，该方法有如下步骤：（1）将电解锰阳极泥30～100℃条件下干燥；（2）粉碎、过筛，使其成粒径不大于0.150mm的粉末状；（3）置于100～400℃条件下灼烧；（4）将步骤（3）处理后的电解锰阳极泥与石墨烯均匀混合，得到电池正极材料；在该电池正极材料中，石墨烯的质量百分数为1.5～4％。在减小污染、资源化利用电解锰阳极泥方面与现有技术相比较，本发明不仅整个操作过程更加简单，关键还在于充满电后的连续放电时间更长。A method for preparing a positive electrode material of a battery using graphene-enhanced electrolytic manganese anode slime, the method has the following steps: (1) drying the electrolytic manganese anode slime at 30-100°C; (2) crushing and sieving to make it into granules (3) burn at 100-400°C; (4) uniformly mix the electrolytic manganese anode slime treated in step (3) with graphene to obtain the positive electrode material of the battery; In the positive electrode material of the battery, the mass percentage of graphene is 1.5-4%. Compared with the prior art in terms of pollution reduction and resource utilization of electrolytic manganese anode slime, the present invention is not only simpler in the whole operation process, but also has a longer continuous discharge time after being fully charged.
Description
技术领域 technical field
本发明涉及利用电解锰阳极泥的来生产电池原料的方法。 The invention relates to a method for producing battery raw materials by utilizing electrolytic manganese anode slime.
背景技术 Background technique
电解锰阳极泥是用电解法生产锰的过程中留存在阳极室内的副产物，由于在电解锰阳极泥中仍然含有含量不可忽视的锰元素（当然也有其他杂质），所以，若将它们清除后而作为废弃物堆存起来或者廉价出售，不仅会造成对环境的污染，同时也造成了锰资源的浪费。因此，为提高锰阳极泥的利用价值，人们就一直在探索资源化利用电解锰阳极泥的各种方法。公告号为CN101717860B、名称为《一种用电解锰阳极泥制备电池原料的方法及其制品》的专利，就是这类探索成果之一。该现有技术采用方法的步骤是，①将电解锰阳极泥干燥至其含水率不高于3％的程度，然后与H2SO4溶液充分混合、充分搅拌；②接着进行固液分离、并用清水洗涤固状物，直至洗涤液中无硫酸根离子为止；③将洗涤后的固状物烘干，直至该烘干固状物的含水率为1～3％；④在烘干固状物中加入离子液体并混合均匀，以得到含活性二氧化锰的原料——即电池正极原料。在资源化利用电解锰阳极泥方面，该现有技术的确取得了不错的技术效果，然而，该现有技术却存在充满电后的连续放电时间还不够长、整个操作过程还约为复杂一点之不足。 Electrolytic manganese anode slime is a by-product left in the anode chamber in the process of producing manganese by electrolysis. Since electrolytic manganese anode slime still contains manganese in a non-negligible content (of course there are other impurities), so if they are removed Pile up as waste or sell it at a low price, which will not only cause environmental pollution, but also cause a waste of manganese resources. Therefore, in order to improve the utilization value of manganese anode slime, people have been exploring various methods for resource utilization of electrolytic manganese anode slime. The patent with the announcement number CN101717860B and the title "A Method for Preparing Battery Raw Materials Using Electrolytic Manganese Anode Slime and Its Products" is one of such exploration results. The steps of the method adopted in the prior art are: ①dry the electrolytic manganese anode slime until its water content is not higher than 3%, and then fully mix and stir it with the H2SO4 solution; ②separate the solid and liquid, and use Wash the solid matter with clean water until there are no sulfate ions in the washing liquid; ③dry the washed solid matter until the moisture content of the dried solid matter is 1-3%; ④dry the solid matter Add the ionic liquid into the mixture and mix evenly to obtain the raw material containing active manganese dioxide—that is, the positive electrode raw material of the battery. In terms of resource utilization of electrolytic manganese anode slime, this prior art has indeed achieved good technical results. However, this prior art has the disadvantages that the continuous discharge time after full charge is not long enough, and the entire operation process is still about a little more complicated. insufficient.
发明内容 Contents of the invention
本发明的目的是提供一种整个操作过程更加简单、充满电后的连续放电时间更长的用石墨烯增强的电解锰阳极泥制备电池正极材料的方法。 The purpose of the present invention is to provide a method for preparing battery anode materials with graphene-enhanced electrolytic manganese anode slime which is simpler in the whole operation process and has a longer continuous discharge time after full charge.
为实现所述目的，提供这样一种用石墨烯增强的电解锰阳极泥制备电池正极材料的方法，与现有技术相同的方面是，该方法包括将首先将电解锰阳极泥作干燥处理的步骤（1）。其改进之处是，所述步骤（1）中的干燥温度为30～100℃；接着进行如下步骤： In order to achieve the stated purpose, there is provided a method for preparing battery anode materials with graphene-enhanced electrolytic manganese anode slime. The same aspect as the prior art is that the method includes the step of first drying the electrolytic manganese anode slime (1). The improvement is that the drying temperature in the step (1) is 30-100°C; then the following steps are carried out:
（2）将干燥后的电解锰阳极泥粉碎、过筛，得到粒径不大于0.150mm的粉末状的电解锰阳极泥； (2) Grinding and sieving the dried electrolytic manganese anode slime to obtain powdery electrolytic manganese anode slime with a particle size not greater than 0.150 mm;
（3）将步骤（2）处理后的电解锰阳极泥置于100～400℃条件下灼烧，时间为1～5小时； (3) Burning the electrolytic manganese anode slime treated in step (2) at 100-400°C for 1-5 hours;
（4）将步骤（3）处理后的电解锰阳极泥与石墨烯均匀混合，得到电池正极材料；在该电池正极材料中，石墨烯的质量百分数为1.5～4％。 (4) Uniformly mixing the electrolytic manganese anode slime treated in step (3) with graphene to obtain a battery positive electrode material; in the battery positive electrode material, the mass percentage of graphene is 1.5-4%.
从方案中可以看出，本发明省略了现有技术中将电解锰阳极泥与硫酸混合，然后又要除尽硫酸根离子的步骤。虽然省略了的这两个步骤可以大体与本发明粉碎与灼烧相抵，但本发明毕竟还是省略了须多准备一种原料的过程。 It can be seen from the scheme that the present invention omits the step of mixing electrolytic manganese anode slime with sulfuric acid and then removing sulfate ions in the prior art. Although these two omitted steps can generally offset the crushing and burning of the present invention, the present invention omits the process of preparing one more raw material after all.
在步骤（3）中对粉末状的电解锰阳极泥进行灼烧，实际上就是通过灼烧来去除含在电解锰阳极泥中的杂质，同时也是将其中不能电解和未被电解的锰均转化为二氧化锰的过程。验证表明，通过灼烧来转化的二氧化锰和电解产生的二氧化锰经过灼烧，会使得这些二氧化锰具有更好的电化学性能更好。在步骤（4）中混合的石墨烯，本身就有独特的电化学性能，在目前，既有通过特殊工艺而生产出的导电型石墨烯之产品，又有石墨烯电池被开发了出来。只是，导电型石墨烯几乎是由百分之百的石墨烯构成；在石墨烯电池中，无论是用量或是作用均只能以石墨烯为主。而在本发明中，仅仅只用了少量的且并不需要特殊工艺来加工的石墨烯。验证表明，在步骤（4）所得的电池正极材料中，如果石墨烯的质量百分数超过4％，充满电后的连续放电时间会大大缩短；在石墨烯的质量百分数低于1.5％的情况下，充满电后的连续放电时间就又比经步骤（3）灼烧处理后的电解锰阳极泥的长不了多少。因此，可以这样认定，在步骤（4）确定的配比范围内，电解锰阳极泥中的二氧化锰与石墨烯存在有相互协同、相互促进的作用，进而能够得到适合使用要求的电池正极材料。验证同样表明，这种相互协同、相互促进的作用还比较大。与现有技术相比较，本发明不仅整个操作过程更加简单，关键还在于充满电后的连续放电时间更长。 Burning the powdered electrolytic manganese anode slime in step (3) is actually to remove the impurities contained in the electrolytic manganese anode slime by burning, and at the same time convert both the manganese that cannot be electrolyzed and the manganese that has not been electrolyzed Process for manganese dioxide. The verification shows that the manganese dioxide converted by burning and the manganese dioxide produced by electrolysis will make these manganese dioxide have better electrochemical performance after burning. The graphene mixed in step (4) itself has unique electrochemical properties. At present, there are not only conductive graphene products produced by special processes, but also graphene batteries have been developed. However, conductive graphene is almost composed of 100% graphene; in graphene batteries, graphene can only be used as the main component in terms of dosage and function. However, in the present invention, only a small amount of graphene that does not require a special process for processing is used. Verification shows that in the battery cathode material obtained in step (4), if the mass percentage of graphene exceeds 4%, the continuous discharge time after full charge will be greatly shortened; The continuous discharge time after being fully charged is not much longer than that of the electrolytic manganese anode slime after the burning treatment in step (3). Therefore, it can be concluded that within the proportioning range determined in step (4), the manganese dioxide and graphene in the electrolytic manganese anode slime have a synergistic and mutually promoting effect, and then a battery cathode material suitable for use can be obtained . Verification also shows that this kind of mutual synergy and mutual promotion is still relatively large. Compared with the prior art, the present invention not only makes the whole operation process simpler, but also lies in the longer continuous discharge time after full charge.
下面结合具体实施方式对本发明作进一步的说明。 The present invention will be further described below in combination with specific embodiments.
具体实施方式 Detailed ways
用石墨烯增强的电解锰阳极泥制备电池正极材料的方法，该方法包括将首先将电解锰阳极泥作干燥处理的步骤（1）。在本发明中，所述步骤（1）中的干燥温度为30～100℃；接着进行如下步骤： A method for preparing battery anode materials with graphene-enhanced electrolytic manganese anode slime, the method includes the step (1) of first drying the electrolytic manganese anode slime. In the present invention, the drying temperature in the step (1) is 30-100°C; then the following steps are carried out:
（2）将干燥后的电解锰阳极泥粉碎、过筛，得到粒径不大于0.150mm的粉末状的电解锰阳极泥； (2) Grinding and sieving the dried electrolytic manganese anode slime to obtain powdery electrolytic manganese anode slime with a particle size not greater than 0.150 mm;
（3）将步骤（2）处理后的电解锰阳极泥置于100～400℃条件下灼烧，时间为1～5小时； (3) Burning the electrolytic manganese anode slime treated in step (2) at 100-400°C for 1-5 hours;
（4）将步骤（3）处理后的电解锰阳极泥与石墨烯均匀混合，得到电池正极材料；在该电池正极材料中，石墨烯的质量百分数为1.5～4％。 (4) Uniformly mixing the electrolytic manganese anode slime treated in step (3) with graphene to obtain a battery positive electrode material; in the battery positive electrode material, the mass percentage of graphene is 1.5-4%.
本发明经过了在实验室的对比性实验验证，验证时所用电解锰阳极泥均来自重庆秀山县同一个电解锰厂。 The invention has been verified by comparative experiments in the laboratory, and the electrolytic manganese anode slime used in the verification is all from the same electrolytic manganese factory in Xiushan County, Chongqing.
对比例采用CN101717860B的《一种用电解锰阳极泥制备电池原料的方法及其制品》所述的方法，除其中“步骤③后所取烘干固状物质量”在对比时只取了20g之外，其余组分与配比的选择和CN101717860B的“例6”相同。 The comparative example adopts the method described in CN101717860B's "A Method for Preparing Battery Raw Materials with Electrolytic Manganese Anode Slime and Products thereof", except that "the amount of dried solid matter obtained after step 3" is only taken from 20g in comparison. Except, the selection of other components and proportioning ratio is the same as "Example 6" of CN101717860B.
本发明的验证过程与上述具体实施方式所述的相同，经步骤（3）处理后的电解锰阳极泥，各验证例均统一取20g，以保证与现有技术有可比性。 The verification process of the present invention is the same as that described in the above specific embodiments. The electrolytic manganese anode slime treated in step (3) is uniformly taken as 20g for each verification example to ensure comparability with the prior art.
上述实验结束后，均用相同的电池性能检测方法来进行检测，验证及检测结果见验证表（为验证表简单、清晰，凡前面已经提及的固定数值均未记载；效果记载与比较，仅列出了最能反应电池正极材料特性和性能的“比容量”和“充满电后的连续放电时间”）。 After the above experiments are over, the same battery performance testing method is used for testing, and the verification and test results are shown in the verification table (for the verification table is simple and clear, all the fixed values mentioned above are not recorded; the effect record and comparison, only The "specific capacity" and "continuous discharge time after full charge" that best reflect the characteristics and performance of the battery's positive electrode material are listed).
验证表： Verification form:
从上述验证例中可以看出，与现有技术相比较，根据本发明方法所制备的以电解锰阳极泥为主要原料的电池正极材料，其比容量和充满电后的连续放电时间这两个主要指标方面，都有了显著提高。尤其是验证例2的记载在该电池正极材料中的石墨烯质量百分数为2％的情况下，提高幅度更大。 As can be seen from the above-mentioned verification examples, compared with the prior art, the battery positive electrode material prepared according to the method of the present invention with electrolytic manganese anode slime as the main raw material has a specific capacity and a continuous discharge time after full charge. The main indicators have all improved significantly. Especially in verification example 2, when the mass percentage of graphene in the positive electrode material of the battery is 2%, the improvement rate is even greater.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510195938.8A CN104746108A (en) | 2015-04-23 | 2015-04-23 | Method for preparing battery anode material by utilizing graphene enhanced electrolytic manganese anode slime |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510195938.8A CN104746108A (en) | 2015-04-23 | 2015-04-23 | Method for preparing battery anode material by utilizing graphene enhanced electrolytic manganese anode slime |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104746108A true CN104746108A (en) | 2015-07-01 |
Family
ID=53586337
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510195938.8A Pending CN104746108A (en) | 2015-04-23 | 2015-04-23 | Method for preparing battery anode material by utilizing graphene enhanced electrolytic manganese anode slime |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104746108A (en) |
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 electrocatalytic 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 nanocomposite electrode material 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 nanocomposite electrode material 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 electrocatalytic 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 | A kind of wastewater electrocatalytic 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 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106159266B (en) | Preparation method of negative electrode slurry for reducing expansion of lithium ion battery | |
| CN103000882B (en) | Lead carbon battery cathode lead plaster and preparation method thereof | |
| CN103540741B (en) | A wet-process forced desulfurization process for lead paste | |
| CN108172922B (en) | A kind of recycling method of positive electrode slurry of semi-solid lithium battery | |
| JP2018526801A (en) | Lithium ion battery negative electrode material, method for producing the same, and lithium ion battery | |
| CN110550611A (en) | Method for efficiently leaching tellurium from copper separating slag of copper anode slime enhanced by external field effect | |
| CN104779403B (en) | Method for improving manganese leaching rate of waste zinc-manganese battery by applying ultrasonic technology | |
| CN104746108A (en) | Method for preparing battery anode material by utilizing graphene enhanced electrolytic manganese anode slime | |
| CN105914375A (en) | Preparation method for molybdenum disulphide or tungsten disulphide and graphene composite material | |
| CN103864073B (en) | The preparation method of Caulis Sacchari sinensis leaf and Sugarcane peel. gac | |
| CN106099096A (en) | Trimanganese tetroxide nano particulate composite that porous carbon supports and preparation method thereof | |
| CN103482690A (en) | Method for synthesizing tetrabasic lead sulfate by utilizing positive electrode waste lead plaster and application thereof | |
| CN107638872A (en) | A kind of flyash/magnetic stalk compound material and preparation method and application | |
| CN113889612B (en) | Carbon-based nano material for lithium battery and preparation method thereof | |
| CN103972502A (en) | Modified cathode material for lithium battery | |
| CN107768762B (en) | A method for recycling the scrapped wet plate of lead-acid battery | |
| CN106140084A (en) | A kind of charing stalk/diatomite molecular sieve demanganization filtrate blending nano-manganese dioxide | |
| CN106185930A (en) | A kind of preparation method of high methylene blue adsorption number carbon content active | |
| CN101717860B (en) | A method for preparing battery raw materials with electrolytic manganese anode slime and its products | |
| CN104241641A (en) | Anode lead plaster of lead-acid accumulator | |
| CN106498167A (en) | A kind of diachylon desulphurization method of intensified by ultrasonic wave ammonium hydrogen carbonate for desulfurizing agent | |
| CN105533397A (en) | Method for reducing rice cadmium content | |
| CN104795572A (en) | Method for preparing lead-graphene composite material | |
| JP2015109254A5 (en) | ||
| CN103143316A (en) | Method for preparing fluorine removal agent by taking perhafnate cement as raw material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20150701 |