CN101927981A - Preparation method of graphite fluoride - Google Patents
Preparation method of graphite fluoride Download PDFInfo
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- CN101927981A CN101927981A CN 201010256264 CN201010256264A CN101927981A CN 101927981 A CN101927981 A CN 101927981A CN 201010256264 CN201010256264 CN 201010256264 CN 201010256264 A CN201010256264 A CN 201010256264A CN 101927981 A CN101927981 A CN 101927981A
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Abstract
The invention discloses a preparation method of graphite fluoride, which is characterized in that an inorganic composite fluorinating agent and a graphite raw material are heated and reacted in the presence of high-purity nitrogen to prepare the graphite fluoride, wherein the inorganic composite fluorinating agent is a mixture of potassium hexafluoromanganate and antimony pentafluoride. By adopting the method, the fluorine content of the finally obtained graphite fluoride can reach 59 percent, the graphite fluoride can be used as a positive electrode material and a solid lubricating material of a lithium ion battery, the purity of the graphite fluoride product prepared by a solid phase method is more than 99 percent, and the utilization value is high; the process has simple operation and high safety, does not need external fluorine gas, and has stable properties of potassium hexafluoromanganate and antimony pentafluoride at normal temperature, thereby having high safety.
Description
Technical field
The present invention relates to the graphite new material technology field, particularly relate to a kind of preparation method of fluorographite.
Background technology
Fluorographite is that hi-tech, high performance graphite material are studied one of focus now, and its chemical formula is CF
x(0.5≤x≤1.3), fluorographite is mainly used in the positive electrode material of solid lubricant and high energy density cells, and its physical and chemical performance is superior.The synthetic method of fluorographite can be divided into following three kinds:
(1) " vapor phase process " high temperature synthetic technology
" vapor phase process " high temperature synthetic technology is the most traditional the most ripe preparation method, in the temperature range of 350 ℃ to 610 ℃ of temperature, adopts graphite raw material directly to contact with the simple substance fluorine gas, and the insulation certain hour prepares (CF)
n(C
2F)
nTwo types fluorographite, temperature of reaction are high more, and product fluorine content is high more, can obtain the product of fluorine carbon ratio greater than 1 more than 600 ℃.
High temperature direct synthesis technique technology is simple, generates CF but follow in the preparation process of producing fluorine gas and fluorographite
4, C
2F
6Perhaps C
3F
8Etc. a large amount of gaseous by-product, there is bigger danger, security is relatively poor.
(2) low-temperature catalyzed synthesis method
Low-temperature catalyzed synthesis method be with volatile fluorides or trace metal fluorochemical as catalyst for reaction, prepare the fluoro-graphite intercalation compound jointly at low temperatures with Graphite Powder 99, fluorine gas and anhydrous HF.The fluoro-graphite intercalation compound that utilizes the catalysis gained is as precursor, and then the feeding fluorine gas carries out fluoridation in 350～600 ℃ of scopes, has obtained the high fluorine fluorographite of fluorine carbon ratio about 1.The temperature of the synthetic fluorographite of this method is lower, and security is higher, but complex technical process, complex operation, the production cycle is longer.
(3) solid-phase synthesis
Fluorine gas is necessary fluorizating agent in the preceding method, and promptly reactive system needs external fluorine gas, and fluorine gas is virulent material, and corrodibility is strong, produces dangerous.Adopt the solid fluorine-containing polymkeric substance to mix, feed in the rare gas element, under different Heating temperatures, reaction times and material proportion condition, prepare fluorographite with different carbon materials.Rare gas element is mainly argon and nitrogen, and carbon material mainly is coke, charcoal, graphite etc., the purity requirement height.
In the preparation method that fluorine gas participates in, all there is big danger in the production of fluorine gas, transportation, the use, there are more side reaction and side reaction product, greatly influenced the quality of fluorographite." solid phase method " technology of preparing is a kind of safe, fluorographite new preparation technology efficiently, show high research prospect, but correlative study does not disclose crucial synthetic technology.
Summary of the invention
The novel method that the purpose of this invention is to provide a kind of " solid phase method " preparation fluorographite, it is to be the method for the synthetic fluorographite of fluorizating agent with the inorganic compounding fluorochemical, by this method, can reduce the potentially dangerous that fluorine gas brings, and prepare fluorographite.
In order to achieve the above object, the technical solution used in the present invention is as follows:
A kind of preparation method of fluorographite, it is to adopt inorganic compounding fluorizating agent and graphite raw material reacting by heating in the presence of high pure nitrogen to make fluorographite, wherein said inorganic compounding fluorizating agent is the mixture of potassium hexafluoromanganate and antimony pentafluoride.
Preparation method of the present invention, the temperature of reaction of wherein said reacting by heating are preferably 360 ℃～550 ℃.
Preparation method of the present invention, wherein said reacting by heating keeps reaction pressure by feeding high pure nitrogen, and initial action pressure is preferably 0.5Mpa～5Mpa.
Preparation method of the present invention, the temperature rise rate of wherein said reacting by heating is 5 ℃/minute～30 ℃/minute, soaking time is 1～4 hour.
Preparation method of the present invention, the high purity graphite raw material of wherein said graphite raw material for using always, as crystalline flake graphite, expanded graphite etc., preferred crystalline flake graphite.
Preparation method of the present invention, wherein the minimum proportional quantity of potassium hexafluoromanganate, antimony pentafluoride and graphite can be calculated as follows:
2K
2MnF
6+4SbF
5→4KSbF
6+2MnF
3+F
2↑
F
2+C→(CF)x
Be K in the inorganic compounding fluorizating agent
2MnF
6: SbF
5=1: 2, described ratio is a mol ratio.
The mass ratio of described inorganic compounding fluorizating agent and graphite raw material is preferably 43: 1～and 143: 1.
Preparation method of the present invention before wherein said method also is included in reaction, carries out the step of leak detection and cleaning by degreasing to the reactive system that adopts.
Preparation method of the present invention before wherein said method also is included in reaction, carries out pretreated step to reaction raw materials, and described pre-treatment step comprises potassium hexafluoromanganate 150 ℃ of vacuum heat-preservings 1 hour, and graphite raw material was 500 ℃ of vacuum heat-preservings 1 hour.
Preparation method of the present invention, wherein said method comprise that also the product that will obtain after the reaction soaks through persalt and vitriolic mixing acid, clean with high purity water again, and vacuum drying obtains fluorographite again.
Preparation method of the present invention, the equipment that wherein is used for described reacting by heating is the Hastelloy manufacturing, the pipeline that is used to connect is a polyfluortetraethylene pipe.Prevent the fluorine gas corrosion.
Further, the invention provides and be used for system for carrying out said process, comprise high pure nitrogen inlet system, reactive system, temperature controller, detachable process furnace, tail gas treatment device, gas piping system, reactive system comprises reactor, platinum resistor temperature measuring device, magnetic stirring apparatus, shotfiring safety valve, tensimeter (A), gas piping system comprise valve (A), valve (B), valve (C), vacuum pump, tensimeter (B).Wherein the reactor in the reactive system, reactor valves (A), valve (B), valve (C), whipping appts are Hastelloy, and other connecting pipelines are polyfluortetraethylene pipe;
Technical scheme of the present invention has following advantage: adopt method of the present invention, the fluorographite fluorine content that finally obtains can reach 59%, can be used as the positive electrode material and the solid lubricant of lithium ion battery, the fluorographite product purity of solid phase method preparation is greater than 99%, and utility value is big; Technological operation of the present invention is simple, and is safe, do not need external fluorine gas, and potassium hexafluoromanganate and antimony pentafluoride be stable in properties at normal temperatures, therefore safe; The present invention can promote the development of crystalline flake graphite deep process technology, is the development of novel material, the new technology guarantee that provides the necessary technical.
Description of drawings
Fig. 1 is present device and schematic flow sheet;
Fig. 2 is the XRD analysis spectrogram of embodiment 1 product;
Fig. 3 is the EDS analysis of spectra of embodiment 1 product;
Fig. 4 is the XRD analysis spectrogram of embodiment 2 products;
Fig. 5 is the EDS analysis of spectra of embodiment 2 products;
Fig. 6 is the XRD analysis spectrogram of embodiment 3 products;
Fig. 7 is the EDS analysis of spectra of embodiment 3 products;
Fig. 8 is the XRD analysis spectrogram of embodiment 4 products;
Fig. 9 is the EDS analysis of spectra of embodiment 4 products;
Wherein: 1-high pure nitrogen bomb, 2-tensimeter (A), 3-vacuum pump, the 4-temperature controller, 5-thermometer resistor, 6-valve (A), 7-valve (B), 8-tensimeter (B), 9-magnetic stirring apparatus, the detachable process furnace of 10-, the 11-absorption bottle, 12-valve (C), 13-reactor, 14-shotfiring safety valve.
Embodiment
Below in conjunction with drawings and Examples, the specific embodiment of the present invention is described in further detail.Following examples are used to illustrate the present invention, but are not used for limiting the scope of the invention.
1, major equipment
The synthesizer flow process that the present invention sets up as shown in Figure 1, mainly comprise several parts such as high pure nitrogen inlet system, reactive system, temperature controller 4, detachable process furnace 10, tail gas treatment device, gas piping system, reactive system comprises reactor 13, platinum resistor temperature measuring device 5, magnetic stirring apparatus 9, shotfiring safety valve 14, tensimeter (A) 2, gas piping system comprise valve (A) 6, valve (B) 7, valve (C) 12, vacuum pump 3, tensimeter (B) 8.
(1) high pure nitrogen inlet system: be high pure nitrogen in the bomb 1, gas cylinder air outlet place is the nitrogen pressure reducer, be communicated with reactor by poly-four fluorine tube, during be provided with valve (A) 6.
(2) reactor 13: reactor material is a Hastelloy, corrosion with fluoro-gas under the opposing high temperature, reactor adopts an end triangle line style to seal firmly, and there are platinum resistor temperature measuring device 5, magnetic stirring apparatus 9 in inside, and there are tensimeter (B) 8 and shotfiring safety valve 14 in the reactor outside.Pack into behind the mixture, sealed reactor 13 adopts outside detachable process furnace 10 heating, temperature controller 4 control temperature rise rate and temperature of reaction.
(3) gas piping system: valve (A) 6, valve (B) 7, valve (C) 12, vacuum pump 3 and poly-four fluorine tube connecting pipeline constitute air-channel system.
(4) tail gas treatment device: tail gas treatment device is connected with reactor 13 by valve (B) 12, and it is the sodium hydroxide solution of the gas absorption bottle 11 interior dress concentration 5%～10% of tetrafluoroethylene material.
2, technical process
The first reactor that uses should adopt scavenging solution to remove the residue of valve, inside reactor and trim earlier to inside reactor and valve cleaning by degreasing.The ligation system pipeline feeds high pure nitrogen, utilizes the resistance to air loss of lather check reactive system.Concrete technological operation is:
(1) with graphite raw material pre-treatment 1 hour under 500 ℃ of temperature of vacuum, the pre-treatment 1 hour under 150 ℃ of temperature of vacuum of potassium hexafluoromanganate powder is preserved down in dry environment.
(2) by proportioning potassium hexafluoromanganate and antimony pentafluoride are mixed, mix with graphite raw material afterwards, the reactor 13 of packing into, find time reactor 13 and gas piping are opened valve (A) 6, and high pure nitrogen is fed reactive system, open valve (B) 7 again, the reactive system of finding time charges into high pure nitrogen, repeatable operation 3～5 times.
(3) feed nitrogen to certain pressure, valve-off (A) 6 is set temperature rise rate and temperature of reaction, and reactor heating 13 is incubated 1～4 hour, stops heating.
(4) reactor cooling is opened valve (C) 12 to normal temperature, feeds high pure nitrogen emptying reactive system, feeds to fill in 5%～10% the sodium hydroxide solution absorption bottle 11.
(5) open reactor, take out reaction product, soak repeatedly with analytical pure hydrochloric acid and dilute sulphuric acid, to PH=6.5, the product of institute descended drying 2 hours for 150 ℃ in vacuum again after drying in convection oven with the high purity deionized water lotion.
3, processing parameter
(1) temperature of reaction
Range of reaction temperature is between 360 ℃～550 ℃, and inorganic compounding fluorochemical and graphite raw material initial reaction temperature are 360 ℃, and temperature is high more, and product fluorine content is high more.
(2) initial action pressure
Before the reaction, the high pure nitrogen inflation pressure is at 0.5Mpa to 5Mpa, and pressure is big more, and product fluorine content is high more.
(3) reaction soaking time
Reaction times can obtain the product of high fluorine carbon ratio in this temperature range between 1 hour to 4 hours, the reaction times, the long quality product that may cause descended.
(4) reaction temperature rise rate
The reactor temperature rise rate has all influenced the fluorine content of thing at higher or lower temperature rise rate between 5～30 ℃/minute.
(5) raw material fluorine carbon proportioning
The quality proportioning of inorganic compounding fluorochemical and graphite raw material is between 43: 1～143: 1, and fluorine carbonaceous amount proportioning is big more, and product fluorine content is high more.
4, product characterizes
The present invention adopts X-ray energy spectrometer (EDS) that product is carried out composition analysis, and EDS belongs to semi-quantitative method, is used for the surface composition analysis, gets a plurality of measured zone in sample, and measure product fluorine carbon ratio is got its mean value.
X-ray diffraction analysis instrument (XRD) characterizes the product crystal structure, in the diffracting spectrum of fluorographite, at 14 ° (2 θ) a strong diffracted ray is arranged, the thickness of the corresponding CF individual layer of this diffracted ray, corresponding crystalline (002) face.When 41 ° to 42 ° (2 θ), this has shown the C-F key length, corresponding crystalline (100) face.Along with the intensification of fluoridation, graphite diminishes at the diffraction peak intensity of 26 ° (2 θ), and diffraction peak narrows down, until fading away.
K in molar ratio
2MnF
6: SbF
5=1: 2 configuration inorganic fluoride mixtures add pretreated crystalline flake graphite, and inorganic compounding fluorochemical and graphite mass ratio are 43: 1.Mixture is moved into reactor, sealed reactor, final inflated with nitrogen pressure 0.5Mpa.15 ℃/minute of the heat-up rates of reactor are set, 500 ℃ of temperature of reaction, 3 hours time, reactor heating, the reaction back off-response device that finishes is cooled to room temperature, takes out reaction product, and the oven dry of purifying obtains product, and product fluorine content is 35.5%.Fig. 2 and Fig. 3 are respectively the XRD analysis spectrogram and the EDS analysis of spectra of products obtained therefrom.
K in molar ratio
2MnF
6: SbF
5=1: 2 configuration inorganic fluoride mixtures add pretreated crystalline flake graphite, and inorganic compounding fluorochemical and graphite mass ratio are 43: 1.Mixture is moved into reactor, sealed reactor, final inflated with nitrogen pressure 2.5Mpa is provided with 15 ℃/minute of reactor temperature rise rates, 500 ℃ of temperature of reaction, 3 hours time, reactor heating, off-response device after reaction finishes, be cooled to room temperature, take out reaction product, the oven dry of purifying obtains product, and product fluorine content is 45.1%.Fig. 4 and Fig. 5 are respectively the XRD analysis spectrogram and the EDS analysis of spectra of products obtained therefrom.
K in molar ratio
2MnF
6: SbF
5=1: 2 configuration inorganic fluoride mixtures add pretreated crystalline flake graphite, and inorganic compounding fluorochemical and graphite mass ratio are 97: 1.Mixture is moved into reactor, sealed reactor, final inflated with nitrogen pressure 5Mpa.20 ℃/minute of the heat-up rates of reactor are set, 500 ℃ of temperature of reaction, 3 hours reaction times, reactor heating, the reaction back off-response device that finishes is cooled to room temperature, takes out reaction product, and the oven dry of purifying obtains product, and product fluorine content is 59.3%.Fig. 6 and Fig. 7 are respectively the XRD analysis spectrogram and the EDS analysis of spectra of products obtained therefrom.
K in molar ratio
2MnF
6: SbF
5=1: 2 configuration inorganic fluoride mixtures add pretreated crystalline flake graphite, and inorganic compounding fluorochemical and graphite mass ratio are 143: 1, and mixture is moved into reactor, sealed reactor, final inflated with nitrogen pressure 5Mpa.20 ℃/minute of the heat-up rates of reactor are set, 500 ℃ of temperature of reaction, 3 hours reaction times, reactor heating, the reaction back off-response device that finishes is cooled to room temperature, takes out reaction product, and the oven dry of purifying obtains product, and product fluorine content is 59.4%.Fig. 8 and Fig. 9 are respectively the XRD analysis spectrogram and the EDS analysis of spectra of products obtained therefrom.
The above only is a preferred implementation of the present invention; should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the technology of the present invention principle; can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (12)
1. the preparation method of a fluorographite is characterized in that, adopts inorganic compounding fluorizating agent and graphite raw material reacting by heating in the presence of high pure nitrogen to make fluorographite, and wherein said inorganic compounding fluorizating agent is the mixture of potassium hexafluoromanganate and antimony pentafluoride.
2. preparation method as claimed in claim 1 is characterized in that, the mass ratio of described inorganic compounding fluorizating agent and graphite raw material is 43: 1～143: 1.
3. preparation method as claimed in claim 1 or 2 is characterized in that, the temperature of reaction of described reacting by heating is 360 ℃～550 ℃.
4. as each described preparation method of claim 1-3, it is characterized in that described reacting by heating keeps reaction pressure by feeding high pure nitrogen, initial action pressure is 0.5Mpa～5Mpa.
5. as each described preparation method of claim 1-4, it is characterized in that the temperature rise rate of described reacting by heating is 5 ℃/minute～30 ℃/minute, soaking time is 1～4 hour.
6. as each described preparation method of claim 1-5, it is characterized in that described graphite raw material is a crystalline flake graphite.
7. as each described preparation method of claim 1-6, it is characterized in that K in the described inorganic compounding fluorizating agent
2MnF
6: SbF
5=1: 2, described ratio is a mol ratio.
8. as each described preparation method of claim 1-7, it is characterized in that, before described method also is included in reaction, the reactive system that adopts is carried out the step of leak detection and cleaning by degreasing.
9. as each described preparation method of claim 1-8, it is characterized in that, before described method also is included in reaction, reaction raw materials is carried out pretreated step, described pre-treatment step comprises potassium hexafluoromanganate 150 ℃ of vacuum heat-preservings 1 hour, and graphite raw material was 500 ℃ of vacuum heat-preservings 1 hour.
10. as each described preparation method of claim 1-9, it is characterized in that described method comprises that also the product that will obtain after the reaction soaks through persalt and vitriolic mixing acid, cleans with high purity water again, vacuum drying obtains fluorographite again.
11., it is characterized in that the equipment that is used for described reacting by heating is the Hastelloy manufacturing as each described preparation method of claim 1-10, the pipeline that is used to connect is a polyfluortetraethylene pipe.
12. be used for each described preparation method's of claim 1-10 system, it is characterized in that, comprise high pure nitrogen inlet system, reactive system, temperature controller, detachable process furnace, tail gas treatment device, gas piping system, reactive system comprises reactor, platinum resistor temperature measuring device, magnetic stirring apparatus, shotfiring safety valve, tensimeter (A), gas piping system comprise valve (A), valve (B), valve (C), vacuum pump, tensimeter (B).
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102447118A (en) * | 2011-11-10 | 2012-05-09 | 江苏环能通环保科技有限公司 | Manufacture equipment for negative electrode material of lithium battery |
| CN102491319A (en) * | 2011-12-16 | 2012-06-13 | 江西东乡高信化工有限公司 | Process for producing graphite fluoride by low-temperature intercalation method |
| CN102677080A (en) * | 2012-03-13 | 2012-09-19 | 张西林 | Graphite atomic nucleus material and processing method thereof |
| CN103043641A (en) * | 2012-11-30 | 2013-04-17 | 东莞市翔丰华电池材料有限公司 | Method for preparing graphite fluoride at low temperature |
| CN108483441A (en) * | 2018-06-01 | 2018-09-04 | 中钢集团新型材料（浙江）有限公司 | Potassium hexafluoromanganate and the antimony pentafluoride system that heat production fluorine gas purifies graphite altogether |
| CN108516543A (en) * | 2018-06-01 | 2018-09-11 | 中钢集团新型材料（浙江）有限公司 | Potassium hexafluoromanganate and the antimony pentafluoride method that heat production fluorine gas purifies graphite altogether |
| CN112871891A (en) * | 2021-01-13 | 2021-06-01 | 哈尔滨科友半导体产业装备与技术研究院有限公司 | Method for cleaning quartz tube of silicon carbide crystal growth furnace |
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| SU1308550A1 (en) * | 1986-01-02 | 1987-05-07 | Предприятие П/Я Г-4567 | Method of producing carbon fluoride |
| CN1733823A (en) * | 2004-08-12 | 2006-02-15 | 杨先金 | High temperature special synthesis method of novel carbon polyfluoride polymer |
| CN1915801A (en) * | 2006-08-24 | 2007-02-21 | 西北核技术研究所 | Technique for synthesizing graphite fluoride and carbon fluoride by using nitrogen trifluoride as fluridizer |
| CN101486454A (en) * | 2008-01-17 | 2009-07-22 | 杨先金 | Industrial novel method for synthesizing graphite fluoride |
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Patent Citations (4)
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| SU1308550A1 (en) * | 1986-01-02 | 1987-05-07 | Предприятие П/Я Г-4567 | Method of producing carbon fluoride |
| CN1733823A (en) * | 2004-08-12 | 2006-02-15 | 杨先金 | High temperature special synthesis method of novel carbon polyfluoride polymer |
| CN1915801A (en) * | 2006-08-24 | 2007-02-21 | 西北核技术研究所 | Technique for synthesizing graphite fluoride and carbon fluoride by using nitrogen trifluoride as fluridizer |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102447118A (en) * | 2011-11-10 | 2012-05-09 | 江苏环能通环保科技有限公司 | Manufacture equipment for negative electrode material of lithium battery |
| CN102491319A (en) * | 2011-12-16 | 2012-06-13 | 江西东乡高信化工有限公司 | Process for producing graphite fluoride by low-temperature intercalation method |
| CN102491319B (en) * | 2011-12-16 | 2012-11-28 | 江西高信科技有限公司 | Process for producing graphite fluoride by low-temperature intercalation method |
| CN102677080A (en) * | 2012-03-13 | 2012-09-19 | 张西林 | Graphite atomic nucleus material and processing method thereof |
| CN103043641A (en) * | 2012-11-30 | 2013-04-17 | 东莞市翔丰华电池材料有限公司 | Method for preparing graphite fluoride at low temperature |
| CN103043641B (en) * | 2012-11-30 | 2014-08-13 | 东莞市翔丰华电池材料有限公司 | Method for preparing graphite fluoride at low temperature |
| CN108483441A (en) * | 2018-06-01 | 2018-09-04 | 中钢集团新型材料（浙江）有限公司 | Potassium hexafluoromanganate and the antimony pentafluoride system that heat production fluorine gas purifies graphite altogether |
| CN108516543A (en) * | 2018-06-01 | 2018-09-11 | 中钢集团新型材料（浙江）有限公司 | Potassium hexafluoromanganate and the antimony pentafluoride method that heat production fluorine gas purifies graphite altogether |
| CN112871891A (en) * | 2021-01-13 | 2021-06-01 | 哈尔滨科友半导体产业装备与技术研究院有限公司 | Method for cleaning quartz tube of silicon carbide crystal growth furnace |
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| CN101927981B (en) | 2012-04-04 |
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