CN102602908A - Purification method of battery-grade graphite fluoride - Google Patents
Purification method of battery-grade graphite fluoride Download PDFInfo
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- CN102602908A CN102602908A CN2012101014002A CN201210101400A CN102602908A CN 102602908 A CN102602908 A CN 102602908A CN 2012101014002 A CN2012101014002 A CN 2012101014002A CN 201210101400 A CN201210101400 A CN 201210101400A CN 102602908 A CN102602908 A CN 102602908A
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Abstract
The invention discloses a purification method of battery-grade graphite fluoride by ultrasonic-assisted HF cleaning. The specific operation steps are as follows: mixing common graphite fluoride with 20% hydrofluoric acid; cleaning for 30-60min under the assistance of ultrasound to fully dissolve impurities; and then, carrying out suction filtration on the system, and drying a filter cake in a heating furnace at the temperature of 150-200 ℃ to obtain the graphite fluoride meeting the battery grade requirement. The invention has the advantages of simple and convenient process, low cost and wide application range, and is beneficial to industrial production.
Description
[ technical field ] A method for producing a semiconductor device
The invention relates to a purification method of graphite fluoride, in particular to a method for removing trace metal ions such as iron, copper, nickel and the like in the graphite fluoride by adopting an ultrasonic-assisted HF (high frequency) washing method so as to enable the graphite fluoride to meet the requirement of a battery grade.
[ background of the invention ]
Graphite fluoride is a graphite intercalation compound synthesized by the direct reaction of carbon and fluorine, and its intercalation is a fluorine atom, and belongs to a covalent bond type intercalation compound. The high fluoridation degree graphite has excellent thermal stability, is an electrical and thermal insulator, is not corroded by strong acid and strong alkali, and has better abrasion life than MoS at any temperature 2 As an additive to lubricating waxes, the bearing load of the parts can be significantly increased and the surface temperature of the lubricated parts can be reduced.
Graphite fluoride, metallic lithium and dissolved LiClO 4 Or LiBF 4 The organic solvent combination of the lithium battery electrode can enable the output voltage and the current density to be much higher than those of common batteries, and the lithium battery electrode has long storage period and wide use temperature range, and forms a high-energy, high-output power and high-density battery. In addition, the graphite fluoride can also be used as a battery anode additive and added into an alkaline zinc-manganese battery, so that the zinc-manganese battery is suitable for discharging under high power; in addition, the actual discharge capacity of the graphite fluoride added with 5 percent during low-power discharge is127% of the theoretical capacity. Recent research results of applying graphite fluoride to high-iron batteries show that the graphite fluoride can remarkably improve the capacity of the batteries and show special electrochemical performance, but the battery materials have high requirements on the purity of the graphite fluoride, such as Fe < 100ppm, cu < 50ppm, ni < 50ppm and the like.
However, the preparation process of CFx is very complex and difficult, and factors influencing the performance of products are many, only a few companies have the ability to produce the products internationally, and the basic research on CFx materials in China is limited to Shanghai organic institute and a few nuclear industry research institutes in China, and no industrial scale is formed. The preparation of the battery-grade graphite fluoride is less researched domestically.
The purification method of graphite mainly comprises the following steps: flotation, alkali-acid method, hydrofluoric acid method, chlorination roasting method, high-temperature purification method, strong acid and strong base and the like. However, in the process of preparing graphite fluoride by using graphite as a raw material, the reaction kettle may be affected, and new impurity ions are introduced, so that the requirement of battery-grade graphite fluoride cannot be met by controlling the purity of graphite, and the product graphite fluoride must be purified again to meet the requirement of battery-grade graphite fluoride. For graphite fluoride, the ultrafine impurities impregnated in the graphite are difficult to remove by a flotation method, the chlorine used by a chlorination roasting method pollutes the environment greatly, the structures of C-F bonds of the graphite fluoride are easy to change by strong acid, strong alkali and a high-temperature method, so that the electricity storage capacity of a battery is influenced, and the graphite fluoride obtained after the treatment still hardly meets the battery grade requirement. HF has F ions, so that the C-F structure can be effectively maintained, and dilute HF can effectively dissolve metal ions such as Fe, ni, cu and the like.
Ultrasonic auxiliary cleaning refers to impacting and stripping dirt on the surface of an object by utilizing the cavitation action of ultrasonic waves so as to achieve the purpose of cleaning. The method has the characteristics of high cleaning cleanliness, high cleaning speed and the like, particularly has incomparable cleaning effect compared with other methods when cleaning fine objects, and is widely applied to various industries due to the advantages. The ultrasonic-assisted HF cleaning method can effectively remove metal ions in the graphite fluoride, so that the graphite fluoride can meet the requirements of battery level.
[ summary of the invention ]
The invention aims to provide a purification process of graphite fluoride, which can meet the battery grade requirement after common graphite fluoride is treated by HF under the ultrasonic-assisted condition.
The invention achieves the purpose through the following scheme: firstly, adding a proper amount of hydrofluoric acid solution into graphite fluoride, and cleaning with the assistance of ultrasound. Generating shock waves by utilizing the cavitation effect of ultrasonic waves, so that HF solution violently impacts graphite fluoride, and impurity ions are stripped; because the cleaning solution contains a large amount of F ions, F in the graphite fluoride is not dissolved into the cleaning solution in the cleaning process, and the C-F structure of the graphite fluoride is not damaged. The addition of cleaning solution can be increased or the above steps can be repeated to further clean and improve the purification capacity. And then, carrying out suction filtration on the cleaned graphite fluoride system, putting the filter cake in a pyrolysis furnace at the temperature of 150-200 ℃, and converting water and redundant HF in the graphite fluoride into gas to volatilize, thus obtaining the battery-grade graphite fluoride.
The invention has the advantages that:
1. ultrasonic auxiliary cleaning is used, the impact of the cleaning liquid on the graphite fluoride is increased by utilizing the cavitation effect of the ultrasonic, the deeply embedded metal ions can be effectively dissolved, and the cleaning effect is greatly improved.
2. The diluted HF solution is used as the cleaning solution, the diluted HF can effectively dissolve various metal ions, and meanwhile, the structure and the fluorine content of the graphite fluoride can be effectively maintained because the cleaning solution contains a large amount of F, and the property of the graphite fluoride is not influenced.
3. Simple operation and low cost. The method comprises the following steps of cleaning common graphite fluoride by using HF under the ultrasonic-assisted condition, and directly carrying out suction filtration and drying.
4. The application range is wide. The method can be used for further purifying the graphite fluoride with the purity of 99-99.9% by increasing the using amount of the cleaning liquid or the cleaning times.
[ detailed description ] embodiments
The following provides a specific embodiment of a method for purifying battery-grade graphite fluoride according to the present invention.
Example 1
100Kg of graphite fluoride with fluorine content of 55-61% and purity of 99.5% is placed in a 400L reaction vessel equipped with a stirrer, 100L of diluted 15% hydrofluoric acid solution is injected, the mixture is uniformly stirred and then placed in ultrasound for 50min, then the filtration is carried out, a filter cake is placed in a hot furnace at 200 ℃ to remove water and residual hydrofluoric acid, the total weight of the product is 99.8Kg, the product is gray, the fluorine content is 55-61%, the impurity ions are Fe < 100ppm, cu < 50ppm and Ni < 50ppm, and the requirements of battery materials are met.
Example 2
100Kg of graphite fluoride with fluorine content of 55-61% and purity of 99.2% is placed in a 400L reaction vessel equipped with a stirrer, 150L of diluted 15% hydrofluoric acid solution is injected, the mixture is uniformly stirred and then placed in ultrasound for 60min, then the filtration is carried out, a filter cake is placed in a hot furnace at 200 ℃ to remove water and residual hydrofluoric acid, the total weight of the product is 100Kg, the product is gray, the fluorine content is 55-61%, the impurity ions are Fe < 100ppm, cu < 50ppm and Ni < 50ppm, and the requirements of battery materials are met.
Example 3
100Kg of graphite fluoride with fluorine content of 50-55% and purity of 99.0% is placed in a 400L reaction vessel equipped with a stirrer, 100L of diluted 20% hydrofluoric acid solution is injected, the mixture is stirred uniformly, then placed in ultrasound for 30min, then filtered, the cleaning step is repeated for 2 times, and finally the filter cake is placed in a hot furnace at 200 ℃ to remove water and residual hydrofluoric acid, wherein the total weight of the product is 99.5Kg, the fluorine content is 50-55%, the impurity ions are Fe < 100ppm, cu < 50ppm and Ni < 50ppm, thus meeting the requirements of battery materials.
Example 4
Putting 200Kg of graphite fluoride with fluorine content of 50-55% and purity of 99.8% in a 600L reaction vessel equipped with a stirrer, injecting 200L of diluted 15% hydrofluoric acid solution, stirring uniformly, then putting in ultrasound, filtering after 40min of ultrasound, putting a filter cake in a 160 ℃ hot furnace to remove water and residual hydrofluoric acid, wherein the total weight of the product is 200Kg, the fluorine content is 50-55%, the impurity ions are Fe < 100ppm, cu < 50ppm and Ni < 50ppm, thus meeting the requirements of battery materials.
The above description is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, many modifications and amendments can be made without departing from the spirit of the present invention, and these modifications and amendments should also be considered as within the scope of the present invention.
Claims (5)
1. A method for purifying battery-grade graphite fluoride. The method is characterized by comprising the following specific steps: putting graphite fluoride and hydrofluoric acid solution into a container, mixing uniformly, then cleaning for 30-60min with the aid of ultrasound, filtering, and putting the filter cake into a heating furnace to remove water and residual hydrofluoric acid, wherein the grey white solid is the purified graphite fluoride.
2. The method for purifying battery-grade graphite fluoride according to claim 1, wherein the graphite fluoride used is graphite fluoride containing 50% -61% fluorine and having a purity of 99.0% -99.9%.
3. The method for purifying battery-grade graphite fluoride according to claim 1, wherein the cleaning solution is 15% -25% hydrofluoric acid, and the water is secondary distilled water or ultrapure water.
4. The purification method of battery-grade graphite fluoride according to claim 1, wherein the ultrasonic frequency is 80kHz-120kHz, and the ultrasonic cleaning time is 30-60 min.
5. The method of claim 1, wherein the container is made of a polymer such as PVC, PE, or PTFE.
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| CN2012101014002A CN102602908A (en) | 2012-04-09 | 2012-04-09 | Purification method of battery-grade graphite fluoride |
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| CN2012101014002A CN102602908A (en) | 2012-04-09 | 2012-04-09 | Purification method of battery-grade graphite fluoride |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103633313A (en) * | 2012-11-13 | 2014-03-12 | 天津锦美碳材科技发展有限公司 | Preparation method for graphite fluoride-lithium manganate composite material and application of same to prepare lithium ion battery as cathode material |
| CN105621398A (en) * | 2015-12-25 | 2016-06-01 | 山东重山光电材料股份有限公司 | Method for preparing high-purity graphite fluoride by catalytic method |
| CN106882805A (en) * | 2017-04-28 | 2017-06-23 | 福建凯昱微晶石墨有限公司 | A kind of micro crystal graphite purifies preparation technology |
| CN106966389A (en) * | 2017-04-28 | 2017-07-21 | 福建凯昱微晶石墨有限公司 | A kind of method of purification of micro crystal graphite |
| CN106966388A (en) * | 2017-04-28 | 2017-07-21 | 福建凯昱微晶石墨有限公司 | A kind of micro crystal graphite high-temperature fluorination method of purification |
| CN107043103A (en) * | 2017-04-28 | 2017-08-15 | 福建凯昱微晶石墨有限公司 | A kind of preparation method of fluorinated graphene |
| CN108793160A (en) * | 2018-08-17 | 2018-11-13 | 广东璞睿泰科环保科技有限公司 | Preparation method with the active Carbon Materials of fluorine removal |
-
2012
- 2012-04-09 CN CN2012101014002A patent/CN102602908A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103633313A (en) * | 2012-11-13 | 2014-03-12 | 天津锦美碳材科技发展有限公司 | Preparation method for graphite fluoride-lithium manganate composite material and application of same to prepare lithium ion battery as cathode material |
| CN103633313B (en) * | 2012-11-13 | 2016-04-06 | 天津锦美碳材科技发展有限公司 | The preparation method of a kind of fluorographite and LiMn2O4 composite material and prepare lithium ion battery as positive electrode |
| CN105621398A (en) * | 2015-12-25 | 2016-06-01 | 山东重山光电材料股份有限公司 | Method for preparing high-purity graphite fluoride by catalytic method |
| CN105621398B (en) * | 2015-12-25 | 2019-08-27 | 山东重山光电材料股份有限公司 | Method for preparing high-purity graphite fluoride by catalytic method |
| CN106882805A (en) * | 2017-04-28 | 2017-06-23 | 福建凯昱微晶石墨有限公司 | A kind of micro crystal graphite purifies preparation technology |
| CN106966389A (en) * | 2017-04-28 | 2017-07-21 | 福建凯昱微晶石墨有限公司 | A kind of method of purification of micro crystal graphite |
| CN106966388A (en) * | 2017-04-28 | 2017-07-21 | 福建凯昱微晶石墨有限公司 | A kind of micro crystal graphite high-temperature fluorination method of purification |
| CN107043103A (en) * | 2017-04-28 | 2017-08-15 | 福建凯昱微晶石墨有限公司 | A kind of preparation method of fluorinated graphene |
| CN108793160A (en) * | 2018-08-17 | 2018-11-13 | 广东璞睿泰科环保科技有限公司 | Preparation method with the active Carbon Materials of fluorine removal |
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