CN108807002A - A kind of preparation method of bioceramic composite porous electrode material - Google Patents
A kind of preparation method of bioceramic composite porous electrode material Download PDFInfo
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- CN108807002A CN108807002A CN201810872192.3A CN201810872192A CN108807002A CN 108807002 A CN108807002 A CN 108807002A CN 201810872192 A CN201810872192 A CN 201810872192A CN 108807002 A CN108807002 A CN 108807002A
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- 239000007772 electrode material Substances 0.000 title claims abstract description 32
- 239000003462 bioceramic Substances 0.000 title claims abstract description 29
- 239000002131 composite material Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 76
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 56
- 238000005245 sintering Methods 0.000 claims abstract description 34
- 229920000168 Microcrystalline cellulose Polymers 0.000 claims abstract description 31
- 235000019813 microcrystalline cellulose Nutrition 0.000 claims abstract description 31
- 239000000463 material Substances 0.000 claims abstract description 30
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 28
- 239000012065 filter cake Substances 0.000 claims abstract description 27
- 230000004913 activation Effects 0.000 claims abstract description 26
- 239000008108 microcrystalline cellulose Substances 0.000 claims abstract description 26
- 229940016286 microcrystalline cellulose Drugs 0.000 claims abstract description 26
- 239000012141 concentrate Substances 0.000 claims abstract description 18
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 18
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 18
- 235000011116 calcium hydroxide Nutrition 0.000 claims abstract description 17
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000005554 pickling Methods 0.000 claims abstract description 15
- 238000001914 filtration Methods 0.000 claims abstract description 14
- 239000000920 calcium hydroxide Substances 0.000 claims abstract description 13
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims abstract description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000010438 heat treatment Methods 0.000 claims abstract description 10
- -1 polytetrafluoroethylene Polymers 0.000 claims abstract description 10
- 238000000748 compression moulding Methods 0.000 claims abstract description 9
- 235000013024 sodium fluoride Nutrition 0.000 claims abstract description 9
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 8
- 238000001816 cooling Methods 0.000 claims abstract description 3
- 238000003756 stirring Methods 0.000 claims abstract description 3
- 238000001291 vacuum drying Methods 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 27
- 239000011261 inert gas Substances 0.000 claims description 21
- 238000005406 washing Methods 0.000 claims description 18
- 235000019441 ethanol Nutrition 0.000 claims description 16
- 125000005909 ethyl alcohol group Chemical group 0.000 claims description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 15
- 238000004321 preservation Methods 0.000 claims description 15
- 238000010792 warming Methods 0.000 claims description 14
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 9
- 229910052698 phosphorus Inorganic materials 0.000 claims description 9
- 239000011574 phosphorus Substances 0.000 claims description 9
- 238000006116 polymerization reaction Methods 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 239000000725 suspension Substances 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical class O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 5
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- 239000005543 nano-size silicon particle Substances 0.000 claims description 4
- 235000012239 silicon dioxide Nutrition 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 239000001307 helium Substances 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- 240000007594 Oryza sativa Species 0.000 claims description 2
- 235000007164 Oryza sativa Nutrition 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- 235000009566 rice Nutrition 0.000 claims description 2
- 239000011775 sodium fluoride Substances 0.000 abstract description 4
- 238000007599 discharging Methods 0.000 abstract description 3
- 238000002156 mixing Methods 0.000 abstract 2
- 239000000243 solution Substances 0.000 description 59
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 36
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 30
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 12
- 239000003610 charcoal Substances 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 238000004140 cleaning Methods 0.000 description 10
- 239000002253 acid Substances 0.000 description 9
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 239000011148 porous material Substances 0.000 description 7
- 239000011521 glass Substances 0.000 description 6
- 229910052742 iron Inorganic materials 0.000 description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 5
- 239000005864 Sulphur Substances 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 238000002390 rotary evaporation Methods 0.000 description 5
- 244000089742 Citrus aurantifolia Species 0.000 description 4
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 4
- 235000011941 Tilia x europaea Nutrition 0.000 description 4
- 210000000481 breast Anatomy 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000004571 lime Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 3
- 229910003978 SiClx Inorganic materials 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- CADZRPOVAQTAME-UHFFFAOYSA-L calcium;hydroxy phosphate Chemical compound [Ca+2].OOP([O-])([O-])=O CADZRPOVAQTAME-UHFFFAOYSA-L 0.000 description 3
- 239000003575 carbonaceous material Substances 0.000 description 3
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 3
- 229910010271 silicon carbide Inorganic materials 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 description 2
- 239000002041 carbon nanotube Substances 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- 150000004679 hydroxides Chemical class 0.000 description 2
- 229910052588 hydroxylapatite Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 206010054949 Metaplasia Diseases 0.000 description 1
- 240000002853 Nelumbo nucifera Species 0.000 description 1
- 235000006508 Nelumbo nucifera Nutrition 0.000 description 1
- 235000006510 Nelumbo pentapetala Nutrition 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000003682 fluorination reaction Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000000413 hydrolysate Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000015689 metaplastic ossification Effects 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000011895 specific detection Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 150000003623 transition metal compounds Chemical class 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
-
- 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
- Y02E60/13—Energy storage using capacitors
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- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Filtering Materials (AREA)
Abstract
The invention discloses a kind of preparation methods of bioceramic composite porous electrode material, belong to technical field of energy material.After the present invention first mixes phosphorus pentoxide, absolute ethyl alcohol and microcrystalline cellulose and sulfuric acid solution, constant temperature is stirred to react, then through being concentrated under reduced pressure, obtains concentrate；After concentrate continuation constant temperature is stirred to react, vacuum drying obtains dried feed；Again by dried feed, hydro-thermal reaction after milk of lime mixing, filtering, pickling is washed, dry, obtains dry pickling filter cake；After dry pickling filter cake and concentrated phosphoric acid are stirred, heating activation is washed using filter, dry, obtains phosphoric acid activation material；Compression moulding after again mixing phosphoric acid activation material, nanometer iron powder, sodium fluoride, polytetrafluoroethylene (PTFE) and absolute ethyl alcohol and stirring, then through high temperature sintering, cooling, discharging is to get bioceramic composite porous electrode material.Bioceramic composite porous electrode material tool electric conductivity prepared by technical solution of the present invention is excellent, porosity and the high feature of specific surface area.
Description
Technical field
The invention discloses a kind of preparation methods of bioceramic composite porous electrode material, belong to energy and material technology neck
Domain.
Background technology
With industrialized fast development, the size of population sharply increase and fossil fuels（Coal, oil and natural gas etc.）
Continuous consumption, getting worse the problems such as energy shortage and environmental pollution.Therefore, it cleanly and efficiently utilizes the energy to become to solve
State the key of problem.Ultracapacitor is a kind of novel electric energy storage device, has power density high（10kWkg-1）, cycle
Long lifespan（>100,000 cycles）And the characteristics such as high rate performance is superior, it is used widely in industry, transport service and military affairs.
There are mainly of two types for ultracapacitor, i.e. double electric layers supercapacitor and fake capacitance ultracapacitor.The former utilizes ion-conductance
The physical absorption of lotus stores electric energy, and wherein electrode material is mainly carbon material, such as activated carbon, graphene and carbon nanotube etc..It
Have excellent electric conductivity, therefore, high rate performance is excellent；But it is limited to its specific surface area, specific capacitance is smaller（<
300Fg-1）, energy density is also smaller（<10Whkg-1）.Fake capacitance ultracapacitor primary transition metal compound, utilizes transition
The valence state changeability energy of metal（Reversible redox reaction）Realize the storage and release of charge.Fake capacitance electrode material compares carbon
Material has higher specific capacitance and energy density, but its poor electric conductivity reduces its high rate performance and power density,
In addition its cycle performance is also poorer than carbon material.Therefore, the performance based on the above two classes capacitor electrode material is developed high performance
C-base composte material becomes the hot spot studied at present.Although emerging graphene and carbon nanotube etc. are much paid close attention to,
Capacitive property is close with activated carbon, and its cost of manufacture is far above activated carbon, so still can not achieve large-scale work at this stage
Industry metaplasia is produced.Also, themselves easily occur to stack phenomenon, especially after compound fake capacitance material, specific surface area substantially declines,
It causes electric double layer effect to be also greatly reduced therewith, is unfavorable for effective hair of double layer capacitor charge-storage effect and fake capacitance effect
It waves.
And traditional porous carbonaceous electrode material, in preparation process, being easy to happen pore structure collapses, and causes porous
Charcoal porosity and specific surface area decline, and the drawbacks of influence product chemical property, therefore, how to make porous electrode materials serve
Better performance becomes the art one of the technical problems that are urgent to solve.
Invention content
The present invention solves the technical problem of：For conventional porous carbonaceous electrode material in preparation process, it is easy
The drawbacks of pore structure occurs to collapse, and porous charcoal porosity and specific surface area is caused to decline, and influences product chemical property,
Provide a kind of preparation method of bioceramic composite porous electrode material.
In order to solve the above-mentioned technical problem, the technical solution adopted in the present invention is：
A kind of preparation method of bioceramic composite porous electrode material, specific preparation process are：
（1）It counts in parts by weight, takes 20~30 parts of phosphorus pentoxides, 60~80 parts of absolute ethyl alcohols, 60~80 parts of crystallite fibres successively
Dimension element, 100~200 parts of sulfuric acid solutions first phosphorus pentoxide, absolute ethyl alcohol and microcrystalline cellulose are added in reaction kettle, Yu Heng
Under warm stirring, sulfuric acid solution is slowly added dropwise, after sulfuric acid solution is added dropwise, continues constant temperature and is stirred to react 4~6h, then pass through
It is concentrated under reduced pressure, obtains concentrate；
（2）After concentrate continuation constant temperature is stirred to react 2~3h, vacuum drying obtains dried feed；
（3）It counts in parts by weight, takes 60~80 parts of dried feeds successively, 8~10 parts of milk of limes, after 4~6h of hydro-thermal reaction, filtering,
Pickling is washed, dry, obtains dry pickling filter cake；
（4）It is 1 in mass ratio by dry pickling filter cake and concentrated phosphoric acid：3~1：After 8 are stirred, heating activation, using filter,
Washing, it is dry, obtain phosphoric acid activation material；
（5）It counts in parts by weight, takes 100~150 parts of phosphoric acid activation material successively, 20~25 parts of nano silicon dioxides, 3~5 parts are received
Rice iron powder, 2~4 parts of sodium fluorides, 20~30 parts of polytetrafluoroethylene (PTFE), 8~10 parts of absolute ethyl alcohols, after being stirred, compression moulding obtains
Blank, then by blank under inert gas shielding state, is warming up to 1400~1500 DEG C, after 3~5h of heat preservation sintering, cooling, alkali
It washes, it is dry, it discharges to get bioceramic composite porous electrode material.
Step（1）The microcrystalline cellulose is the microcrystalline cellulose that levelling off degree of polymerization is 100~180.
Step（1）The sulfuric acid solution is the sulfuric acid solution that mass fraction is 45~50%.
Step（1）It is described to be slowly added dropwise to be added dropwise with 6~8mL/min rates.
Step（3）The milk of lime is that mass concentration is 100~180g/L calcium hydroxide suspensions.
Step（4）The heating activates：360~380 DEG C are warming up to 3~5 DEG C/min rate programs, heat preservation activation 3
~5h.
Step（5）The inert gas is any one in nitrogen, helium or argon gas.
The beneficial effects of the invention are as follows：
（1）Technical solution of the present invention is urged first using phosphorus pentoxide, absolute ethyl alcohol and microcrystalline cellulose as raw material in sulfuric acid solution
Under the conditions of change, make microcrystalline cellulose that hydro-thermal charing gradually occur, and with the concentration of sulfuric acid solution, after concentration improves, catalysis five
It aoxidizes two phosphorus and absolute ethyl alcohol dehydration generates phosphatide, phosphatide can issue unboiled water solution, hydrolysate and calcium in milk of lime alkaline condition
Ions binding increasingly generates calcium hydroxy phosphate, and once having calcium hydroxy phosphate nucleus to generate can be by microcrystalline cellulose reaction generation
Hydro-thermal charcoal absorption, to make calcium hydroxy phosphate crystal with nanocrystal fine dispersion in hydro-thermal charcoal pore structure, and rear
During continuous phosphoric acid activation, with the raising of temperature, further dehydration and cross-linking reaction occur inside hydro-thermal charcoal, in hydro-thermal charcoal
Inside forms abundant pore structure, and the hydroxyapatite that the cross-linked network of formation can adsorb hydro-thermal charcoal is further secured to friendship
Join in network structure, so that it is played good humidification, avoid pore structure under hot conditions from collapsing, make porosity and ratio
Surface area is effectively kept；
（2）Technical solution of the present invention makes the hydroxyapatite disperseed in pore structure occur by using further high-temperature process
Sintering forms bioceramic, to form bioceramic supporting layer in porous carbonaceous inside configuration hole, effectively plays reinforcement
Effect, and under nanometer iron powder and sodium fluoride catalytic condition, silica and carbon in system can be made to react raw under the high temperature conditions
At silicon carbide, the generation of silicon carbide is conducive to form carbon-chemistry of silicones key between porous charcoal and biological ceramic layer, effectively improve
Interface compatibility between porous charcoal and biological ceramic layer, in addition, since the presence of iron ion and sodium fluoride is, it can be achieved that carbonization
The doping of silicon, and the electric conductivity of silicon carbide goes up not down with the decline of purity, is improving the boundary between porous charcoal and bioceramic
While the binding force of face, interference of the electric conductivity decline to product chemical property at interface cohesion is effectively prevented.
Specific implementation mode
It counts in parts by weight, takes 20~30 parts of phosphorus pentoxides, 60~80 parts of absolute ethyl alcohols, 60~80 parts of crystallite fibres successively
Dimension element, 100~200 parts of sulfuric acid solutions first phosphorus pentoxide, absolute ethyl alcohol and microcrystalline cellulose are added in reaction kettle, Yu Wen
Degree is 85~90 DEG C, under the conditions of rotating speed is 300~500r/min, when constant temperature is stirred by dropping funel with 6~8mL/min speed
Sulfuric acid solution is added dropwise in reaction kettle by rate, after sulfuric acid solution is added dropwise, is continued constant temperature and is stirred to react 4~6h, wait reacting
Terminate, material in reaction kettle is transferred in Rotary Evaporators, is 75~85 DEG C in temperature, pressure is 400~500mmHg conditions
Under, 45~60min is concentrated under reduced pressure, obtains concentrate, then by concentrate in temperature is 85~90 DEG C, speed of agitator is 400~600r/
It it is 100 DEG C in temperature, under the conditions of vacuum degree is 0.093MPa, vacuum is dry after continuation constant temperature is stirred to react 2~3h under the conditions of min
It is dry to constant weight, obtain dried feed；It counts in parts by weight, takes 60~80 parts of dried feeds, 8~10 parts of milk of limes that water heating kettle is added successively
In, it is 170~185 DEG C in temperature, under the conditions of rotating speed is 400~600r/min, after 4~6h of hydro-thermal reaction, filtering obtains filter cake,
It is used in combination the acetic acid that mass fraction is 3~5% to wash 4~8 times, then the filter cake after acetic acid is washed is washed with deionized to washing
Liquid is in neutrality, then by the filter cake after washing under the conditions of temperature is 105~110 DEG C, dry to constant weight, obtains dry pickling filter cake；
It is 1 in mass ratio that gained, which is dried the concentrated phosphoric acid that pickling filter cake and mass fraction are 85%,：3~1：8 pour into crucible, use glass
After stick is stirred 10~15min, crucible is moved into Muffle furnace, 360~380 are warming up to 3~5 DEG C/min rate programs
DEG C, after keeping the temperature 3~5h of activation, filtering obtains filter residue, and filter residue is washed with deionized until cleaning solution is in neutrality, then will be washed
Filter residue afterwards is transferred in baking oven, is dried to constant weight under the conditions of being 105~110 DEG C in temperature, is obtained phosphoric acid activation material；In parts by weight
Meter takes 100~150 parts of phosphoric acid activation material, 20~25 parts of nano silicon dioxides, 3~5 parts of nanometer iron powders, 2~4 parts of fluorinations successively
Sodium, 20~30 parts of polytetrafluoroethylene (PTFE), 8~10 parts of absolute ethyl alcohols, 45 are stirred with 600~700r/min rotating speeds with blender~
After 60min, under the conditions of pressure is 8~15MPa, compression moulding obtains blank, then blank is transferred in sintering furnace, with 600~
800L/min rates are passed through inert gas into stove, under inert gas shielding state, are heated up with 8~10 DEG C/min rate programs
To 1400~1500 DEG C, after 3~5h of heat preservation sintering, room temperature is cooled to the furnace, discharge, obtain sintering feed, and gained sintering feed is used
The sodium hydroxide solution that mass fraction is 10~15% washs 3~5 times, then the sintering feed deionization after sodium hydroxide is washed
It is dry to get bioceramic composite porous electrode material after water washing 4~6 times.The microcrystalline cellulose is that levelling off degree of polymerization is
100~180 microcrystalline cellulose.The sulfuric acid solution is the sulfuric acid solution that mass fraction is 45~50%.The milk of lime is matter
Measure a concentration of 100~180g/L calcium hydroxides suspension.The inert gas is any one in nitrogen, helium or argon gas.
It counts in parts by weight, takes 30 parts of phosphorus pentoxides, 80 parts of absolute ethyl alcohols, 80 parts of microcrystalline celluloses, 200 parts of sulphur successively
First phosphorus pentoxide, absolute ethyl alcohol and microcrystalline cellulose are added in reaction kettle for acid solution, are 90 DEG C in temperature, rotating speed is
Under the conditions of 500r/min, sulfuric acid solution is added dropwise in reaction kettle with 8mL/min rates by dropping funel when constant temperature is stirred,
After sulfuric acid solution is added dropwise, continues constant temperature and be stirred to react 6h, to the end of reaction, material in reaction kettle is transferred to rotary evaporation
In instrument, it is 85 DEG C in temperature, under the conditions of pressure is 500mmHg, 60min is concentrated under reduced pressure, obtains concentrate, then by concentrate in temperature
It is 90 DEG C, is 100 DEG C in temperature, vacuum degree is after continuation constant temperature is stirred to react 3h under the conditions of speed of agitator is 600r/min
Under the conditions of 0.093MPa, it is dried under vacuum to constant weight, obtains dried feed；It counts in parts by weight, takes 80 parts of dried feeds, 10 parts of lime successively
Breast is added in water heating kettle, is 185 DEG C in temperature, and under the conditions of rotating speed is 600r/min, after hydro-thermal reaction 6h, filtering obtains filter cake,
It is used in combination the acetic acid that mass fraction is 5% to wash 8 times, then the filter cake after acetic acid is washed is washed with deionized in being in cleaning solution
Property, then under the conditions of being 110 DEG C in temperature by the filter cake after washing, it is dry to constant weight, obtain dry pickling filter cake；Gained is dried into acid
The concentrated phosphoric acid that filter wash cake and mass fraction are 85% is 1 in mass ratio：8 pour into crucible, after being stirred 15min with glass bar,
Crucible is moved into Muffle furnace, is warming up to 380 DEG C, after heat preservation activates 5h with 5 DEG C/min rate programs, filtering obtains filter residue, is used in combination
Filter residue after washing then is transferred in baking oven until cleaning solution is in neutrality by deionized water washing filter residue, in temperature be 110 DEG C of conditions
Lower drying obtains phosphoric acid activation material to constant weight；It counts in parts by weight, takes 150 parts of phosphoric acid activation material, 20~25 parts of nano-silicas successively
SiClx, 5 parts of nanometer iron powders, 4 parts of sodium fluorides, 30 parts of polytetrafluoroethylene (PTFE), 10 parts of absolute ethyl alcohols, with blender with 700r/min rotating speeds
After being stirred 60min, under the conditions of pressure is 15MPa, compression moulding obtains blank, then blank is transferred in sintering furnace, with
800L/min rates are passed through inert gas into stove, under inert gas shielding state, are warming up to 10 DEG C/min rate programs
It 1500 DEG C, after heat preservation sintering 5h, cools to room temperature with the furnace, discharges, obtain sintering feed, and be 10 by gained sintering feed mass fraction
~15% sodium hydroxide solution washs 3~5 times, then the sintering feed after sodium hydroxide is washed is washed with deionized 4~6 times
Afterwards, it dries to get bioceramic composite porous electrode material.The microcrystalline cellulose is that the crystallite that levelling off degree of polymerization is 180 is fine
Dimension element.The sulfuric acid solution is the sulfuric acid solution that mass fraction is 50%.The milk of lime is that mass concentration is 180g/L hydroxides
Calcium suspension.The inert gas is nitrogen.
It counts in parts by weight, takes 30 parts of phosphorus pentoxides, 80 parts of absolute ethyl alcohols, 80 parts of microcrystalline celluloses, 200 parts of sulphur successively
First phosphorus pentoxide, absolute ethyl alcohol and microcrystalline cellulose are added in reaction kettle for acid solution, are 90 DEG C in temperature, rotating speed is
Under the conditions of 500r/min, sulfuric acid solution is added dropwise in reaction kettle with 8mL/min rates by dropping funel when constant temperature is stirred,
After sulfuric acid solution is added dropwise, continues constant temperature and be stirred to react 6h, to the end of reaction, material in reaction kettle is transferred to rotary evaporation
In instrument, it is 85 DEG C in temperature, under the conditions of pressure is 500mmHg, 60min is concentrated under reduced pressure, obtains concentrate, then by concentrate in temperature
It is 90 DEG C, is 100 DEG C in temperature, vacuum degree is after continuation constant temperature is stirred to react 3h under the conditions of speed of agitator is 600r/min
Under the conditions of 0.093MPa, it is dried under vacuum to constant weight, obtains dried feed；It counts in parts by weight, takes 80 parts of dried feeds, 10 parts of lime successively
Breast is added in water heating kettle, is 185 DEG C in temperature, and under the conditions of rotating speed is 600r/min, after hydro-thermal reaction 6h, filtering obtains filter cake,
It is used in combination the acetic acid that mass fraction is 5% to wash 8 times, then the filter cake after acetic acid is washed is washed with deionized in being in cleaning solution
Property, then under the conditions of being 110 DEG C in temperature by the filter cake after washing, it is dry to constant weight, obtain dry pickling filter cake；Gained is dried into acid
The concentrated phosphoric acid that filter wash cake and mass fraction are 85% is 1 in mass ratio：8 pour into crucible, after being stirred 15min with glass bar,
Crucible is moved into Muffle furnace, is warming up to 380 DEG C, after heat preservation activates 5h with 5 DEG C/min rate programs, filtering obtains filter residue, is used in combination
Filter residue after washing then is transferred in baking oven until cleaning solution is in neutrality by deionized water washing filter residue, in temperature be 110 DEG C of conditions
Lower drying obtains phosphoric acid activation material to constant weight；It counts in parts by weight, takes 150 parts of phosphoric acid activation material, 20~25 parts of nano-silicas successively
SiClx, 30 parts of polytetrafluoroethylene (PTFE), 10 parts of absolute ethyl alcohols, after being stirred 60min with blender with 700r/min rotating speeds, in pressure
Under the conditions of 15MPa, compression moulding obtains blank, then blank is transferred in sintering furnace, is passed through into stove with 800L/min rates lazy
Property gas is warming up to 1500 DEG C, after heat preservation sintering 5h, with stove under inert gas shielding state with 10 DEG C/min rate programs
It is cooled to room temperature, discharges, obtain sintering feed, and gained sintering feed is washed 3 with the sodium hydroxide solution that mass fraction is 10~15%
~5 times, then after sintering feed after sodium hydroxide is washed is washed with deionized 4~6 times, drying is compound to get bioceramic
Porous electrode material.The microcrystalline cellulose is the microcrystalline cellulose that levelling off degree of polymerization is 180.The sulfuric acid solution is quality point
The sulfuric acid solution that number is 50%.The milk of lime is that mass concentration is 180g/L calcium hydroxide suspensions.The inert gas is nitrogen
Gas.
It counts in parts by weight, takes 30 parts of phosphorus pentoxides, 80 parts of absolute ethyl alcohols, 80 parts of microcrystalline celluloses, 200 parts of sulphur successively
First phosphorus pentoxide, absolute ethyl alcohol and microcrystalline cellulose are added in reaction kettle for acid solution, are 90 DEG C in temperature, rotating speed is
Under the conditions of 500r/min, sulfuric acid solution is added dropwise in reaction kettle with 8mL/min rates by dropping funel when constant temperature is stirred,
After sulfuric acid solution is added dropwise, continues constant temperature and be stirred to react 6h, to the end of reaction, material in reaction kettle is transferred to rotary evaporation
In instrument, it is 85 DEG C in temperature, under the conditions of pressure is 500mmHg, 60min is concentrated under reduced pressure, obtains concentrate, then by concentrate in temperature
It is 90 DEG C, is 100 DEG C in temperature, vacuum degree is after continuation constant temperature is stirred to react 3h under the conditions of speed of agitator is 600r/min
Under the conditions of 0.093MPa, it is dried under vacuum to constant weight, obtains dried feed；It counts in parts by weight, takes 80 parts of dried feeds, 10 parts of lime successively
Breast is added in water heating kettle, is 185 DEG C in temperature, and under the conditions of rotating speed is 600r/min, after hydro-thermal reaction 6h, filtering obtains filter cake,
It is used in combination the acetic acid that mass fraction is 5% to wash 8 times, then the filter cake after acetic acid is washed is washed with deionized in being in cleaning solution
Property, then under the conditions of being 110 DEG C in temperature by the filter cake after washing, it is dry to constant weight, obtain dry pickling filter cake；Gained is dried into acid
The concentrated phosphoric acid that filter wash cake and mass fraction are 85% is 1 in mass ratio：8 pour into crucible, after being stirred 15min with glass bar,
Crucible is moved into Muffle furnace, is warming up to 380 DEG C, after heat preservation activates 5h with 5 DEG C/min rate programs, filtering obtains filter residue, is used in combination
Filter residue after washing then is transferred in baking oven until cleaning solution is in neutrality by deionized water washing filter residue, in temperature be 110 DEG C of conditions
Lower drying obtains phosphoric acid activation material to constant weight；It counts in parts by weight, takes 150 parts of phosphoric acid activation material successively, 5 parts of nanometer iron powders, 4 parts
Sodium fluoride, 30 parts of polytetrafluoroethylene (PTFE), 10 parts of absolute ethyl alcohols, after being stirred 60min with blender with 700r/min rotating speeds, in pressure
Under the conditions of power is 15MPa, compression moulding obtains blank, then blank is transferred in sintering furnace, is passed through into stove with 800L/min rates
Inert gas is warming up to 1500 DEG C under inert gas shielding state with 10 DEG C/min rate programs, after heat preservation sintering 5h, with
Stove is cooled to room temperature, discharging, obtains sintering feed, and gained sintering feed is washed with the sodium hydroxide solution that mass fraction is 10~15%
It washs 3~5 times, then after the sintering feed after sodium hydroxide is washed is washed with deionized 4~6 times, it is dry multiple to get bioceramic
Close porous electrode material.The microcrystalline cellulose is the microcrystalline cellulose that levelling off degree of polymerization is 180.The sulfuric acid solution is quality
The sulfuric acid solution that score is 50%.The milk of lime is that mass concentration is 180g/L calcium hydroxide suspensions.The inert gas is
Nitrogen.
It counts in parts by weight, takes 30 parts of phosphorus pentoxides, 80 parts of absolute ethyl alcohols, 80 parts of microcrystalline celluloses, 200 parts of sulphur successively
First phosphorus pentoxide, absolute ethyl alcohol and microcrystalline cellulose are added in reaction kettle for acid solution, are 90 DEG C in temperature, rotating speed is
Under the conditions of 500r/min, sulfuric acid solution is added dropwise in reaction kettle with 8mL/min rates by dropping funel when constant temperature is stirred,
After sulfuric acid solution is added dropwise, continues constant temperature and be stirred to react 6h, to the end of reaction, material in reaction kettle is transferred to rotary evaporation
In instrument, it is 85 DEG C in temperature, under the conditions of pressure is 500mmHg, 60min is concentrated under reduced pressure, obtains concentrate, then by concentrate in temperature
It is 90 DEG C, is 100 DEG C in temperature, vacuum degree is after continuation constant temperature is stirred to react 3h under the conditions of speed of agitator is 600r/min
Under the conditions of 0.093MPa, it is dried under vacuum to constant weight, obtains dried feed；It counts in parts by weight, takes 80 parts of dried feeds, 10 parts of lime successively
Breast is added in water heating kettle, is 185 DEG C in temperature, and under the conditions of rotating speed is 600r/min, after hydro-thermal reaction 6h, filtering obtains filter cake,
It is used in combination the acetic acid that mass fraction is 5% to wash 8 times, then the filter cake after acetic acid is washed is washed with deionized in being in cleaning solution
Property, then under the conditions of being 110 DEG C in temperature by the filter cake after washing, it is dry to constant weight, obtain dry pickling filter cake；Gained is dried into acid
The concentrated phosphoric acid that filter wash cake and mass fraction are 85% is 1 in mass ratio：8 pour into crucible, after being stirred 15min with glass bar,
Crucible is moved into Muffle furnace, is warming up to 380 DEG C, after heat preservation activates 5h with 5 DEG C/min rate programs, filtering obtains filter residue, is used in combination
Filter residue after washing then is transferred in baking oven until cleaning solution is in neutrality by deionized water washing filter residue, in temperature be 110 DEG C of conditions
Lower drying obtains phosphoric acid activation material to constant weight；It counts in parts by weight, takes 150 parts of phosphoric acid activation material, 20~25 parts of nano-silicas successively
SiClx, 5 parts of nanometer iron powders, 4 parts of sodium fluorides, 30 parts of polytetrafluoroethylene (PTFE), 10 parts of absolute ethyl alcohols, with blender with 700r/min rotating speeds
After being stirred 60min, under the conditions of pressure is 15MPa, compression moulding obtains blank, then blank is transferred in sintering furnace, with
800L/min rates are passed through inert gas into stove, under inert gas shielding state, are warming up to 10 DEG C/min rate programs
It 800 DEG C, after heat preservation sintering 5h, cools to room temperature with the furnace, discharges, obtain sintering feed, and be 10 by gained sintering feed mass fraction
~15% sodium hydroxide solution washs 3~5 times, then the sintering feed after sodium hydroxide is washed is washed with deionized 4~6 times
Afterwards, it dries to get bioceramic composite porous electrode material.The microcrystalline cellulose is that the crystallite that levelling off degree of polymerization is 180 is fine
Dimension element.The sulfuric acid solution is the sulfuric acid solution that mass fraction is 50%.The milk of lime is that mass concentration is 180g/L hydroxides
Calcium suspension.The inert gas is nitrogen.
It counts in parts by weight, takes 30 parts of phosphorus pentoxides, 80 parts of absolute ethyl alcohols, 80 parts of microcrystalline celluloses, 200 parts of sulphur successively
First phosphorus pentoxide, absolute ethyl alcohol and microcrystalline cellulose are added in reaction kettle for acid solution, are 90 DEG C in temperature, rotating speed is
Under the conditions of 500r/min, sulfuric acid solution is added dropwise in reaction kettle with 8mL/min rates by dropping funel when constant temperature is stirred,
After sulfuric acid solution is added dropwise, continues constant temperature and be stirred to react 6h, to the end of reaction, material in reaction kettle is transferred to rotary evaporation
In instrument, it is 85 DEG C in temperature, under the conditions of pressure is 500mmHg, 60min is concentrated under reduced pressure, obtains concentrate, then by concentrate in temperature
It is 90 DEG C, is 100 DEG C in temperature, vacuum degree is after continuation constant temperature is stirred to react 3h under the conditions of speed of agitator is 600r/min
Under the conditions of 0.093MPa, it is dried under vacuum to constant weight, obtains dried feed；The concentrated phosphoric acid that gained dried feed and mass fraction are 85% is pressed
Mass ratio is 1：8 pour into crucible, and after being stirred 15min with glass bar, crucible is moved into Muffle furnace, with 5 DEG C/min speed
To 380 DEG C, after heat preservation activation 5h, filtering obtains filter residue, and filter residue is washed with deionized in cleaning solution is in for rate temperature programming
Property, then the filter residue after washing is transferred in baking oven, it is dried to constant weight under the conditions of being 110 DEG C in temperature, obtains phosphoric acid activation material；By weight
Number meter is measured, takes 150 parts of phosphoric acid activation material successively, 20~25 parts of nano silicon dioxides, 5 parts of nanometer iron powders, 4 parts of sodium fluorides, 30
Part polytetrafluoroethylene (PTFE), 10 parts of absolute ethyl alcohols, after being stirred 60min with blender with 700r/min rotating speeds, in pressure be 15MPa
Under the conditions of, compression moulding obtains blank, then blank is transferred in sintering furnace, and inert gas is passed through into stove with 800L/min rates,
Under inert gas shielding state, it is warming up to 1500 DEG C with 10 DEG C/min rate programs, after heat preservation sintering 5h, cools to room with the furnace
Temperature, discharging obtain sintering feed, and gained sintering feed are washed 3~5 times with the sodium hydroxide solution that mass fraction is 10~15%, then
It is dry to get bioceramic composite porous electrode after sintering feed after sodium hydroxide is washed is washed with deionized 4~6 times
Material.The microcrystalline cellulose is the microcrystalline cellulose that levelling off degree of polymerization is 180.The sulfuric acid solution is that mass fraction is 50%
Sulfuric acid solution.The inert gas is nitrogen.
Comparative example：The porous electrode material of Shanghai Science and Technology Ltd. production.
The bioceramic composite porous electrode material and comparative example product of example 1 to 5 gained of example are subjected to performance detection,
Specific detection method is as follows：
Electrochemical property test uses three traditional electrode testing devices, with 6molL-1KOH solution as electrolyte,
It is carried out in CHI660D electrochemical workstations, wherein working electrode is the porous carbon electrode being prepared, and reference electrode is that saturation is sweet
Mercury electrode（SCE）, auxiliary electrode is platinum plate electrode.It has been substantially carried out cyclic voltammetric（CV）Test and constant current charge-discharge（GCD）
The sweep speed of test, cyclic voltammetry is 10-50mVs-1, the current density of constant current charge-discharge test is 0.625-
3.125Ag-1Voltage window is -1.1- (- 0.1) V.The pore structure of porous charcoal is tested using full-automatic surface physical adsorption appearance
Matter.
Specific testing result is as shown in table 1：
The 1 specific testing result of bioceramic composite porous electrode material of table
By 1 testing result of table it is found that bioceramic composite porous electrode material prepared by technical solution of the present invention has electric conductivity
Excellent, porosity and the high feature of specific surface area have broad prospects in the development of energy and material technology industry.
Claims (7)
1. a kind of preparation method of bioceramic composite porous electrode material, it is characterised in that specifically preparation process is：
（1）It counts in parts by weight, takes 20~30 parts of phosphorus pentoxides, 60~80 parts of absolute ethyl alcohols, 60~80 parts of crystallite fibres successively
Dimension element, 100~200 parts of sulfuric acid solutions first phosphorus pentoxide, absolute ethyl alcohol and microcrystalline cellulose are added in reaction kettle, Yu Heng
Under warm stirring, sulfuric acid solution is slowly added dropwise, after sulfuric acid solution is added dropwise, continues constant temperature and is stirred to react 4~6h, then pass through
It is concentrated under reduced pressure, obtains concentrate；
（2）After concentrate continuation constant temperature is stirred to react 2~3h, vacuum drying obtains dried feed；
（3）It counts in parts by weight, takes 60~80 parts of dried feeds successively, 8~10 parts of milk of limes, after 4~6h of hydro-thermal reaction, filtering,
Pickling is washed, dry, obtains dry pickling filter cake；
（4）It is 1 in mass ratio by dry pickling filter cake and concentrated phosphoric acid：3~1：After 8 are stirred, heating activation, using filter,
Washing, it is dry, obtain phosphoric acid activation material；
（5）It counts in parts by weight, takes 100~150 parts of phosphoric acid activation material successively, 20~25 parts of nano silicon dioxides, 3~5 parts are received
Rice iron powder, 2~4 parts of sodium fluorides, 20~30 parts of polytetrafluoroethylene (PTFE), 8~10 parts of absolute ethyl alcohols, after being stirred, compression moulding obtains
Blank, then by blank under inert gas shielding state, is warming up to 1400~1500 DEG C, after 3~5h of heat preservation sintering, cooling, alkali
It washes, it is dry, it discharges to get bioceramic composite porous electrode material.
2. a kind of preparation method of bioceramic composite porous electrode material according to claim 1, which is characterized in that step
Suddenly（1）The microcrystalline cellulose is the microcrystalline cellulose that levelling off degree of polymerization is 100~180.
3. a kind of preparation method of bioceramic composite porous electrode material according to claim 1, which is characterized in that step
Suddenly（1）The sulfuric acid solution is the sulfuric acid solution that mass fraction is 45~50%.
4. a kind of preparation method of bioceramic composite porous electrode material according to claim 1, which is characterized in that step
Suddenly（1）It is described to be slowly added dropwise to be added dropwise with 6~8mL/min rates.
5. a kind of preparation method of bioceramic composite porous electrode material according to claim 1, which is characterized in that step
Suddenly（3）The milk of lime is that mass concentration is 100~180g/L calcium hydroxide suspensions.
6. a kind of preparation method of bioceramic composite porous electrode material according to claim 1, which is characterized in that step
Suddenly（4）The heating activates：360~380 DEG C are warming up to 3~5 DEG C/min rate programs, 3~5h of heat preservation activation.
7. a kind of preparation method of bioceramic composite porous electrode material according to claim 1, which is characterized in that step
Suddenly（5）The inert gas is any one in nitrogen, helium or argon gas.
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