CN103879983B - Method for modifying carbon material for electrode and carbon material for electrode produced by same - Google Patents
Method for modifying carbon material for electrode and carbon material for electrode produced by same Download PDFInfo
- Publication number
- CN103879983B CN103879983B CN201210585459.3A CN201210585459A CN103879983B CN 103879983 B CN103879983 B CN 103879983B CN 201210585459 A CN201210585459 A CN 201210585459A CN 103879983 B CN103879983 B CN 103879983B
- Authority
- CN
- China
- Prior art keywords
- carbon material
- electrode
- titanium dioxide
- modifying
- carbon
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 70
- 239000007772 electrode material Substances 0.000 title claims abstract description 13
- 238000000034 method Methods 0.000 title claims description 32
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 164
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 64
- 239000002904 solvent Substances 0.000 claims abstract description 30
- 238000010438 heat treatment Methods 0.000 claims abstract description 28
- 239000002243 precursor Substances 0.000 claims abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 claims abstract description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000010612 desalination reaction Methods 0.000 claims abstract description 4
- 239000003990 capacitor Substances 0.000 claims abstract description 3
- 238000004146 energy storage Methods 0.000 claims abstract description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 106
- 239000011259 mixed solution Substances 0.000 claims description 42
- 239000013078 crystal Substances 0.000 claims description 34
- 230000001476 alcoholic effect Effects 0.000 claims description 25
- 239000000155 melt Substances 0.000 claims description 14
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 13
- 230000008018 melting Effects 0.000 claims description 12
- 238000002844 melting Methods 0.000 claims description 12
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 11
- -1 quaternary ammonium halide Chemical group 0.000 claims description 10
- 239000001763 2-hydroxyethyl(trimethyl)azanium Substances 0.000 claims description 9
- 235000019743 Choline chloride Nutrition 0.000 claims description 9
- 229910052799 carbon Inorganic materials 0.000 claims description 9
- 229960003178 choline chloride Drugs 0.000 claims description 9
- SGMZJAMFUVOLNK-UHFFFAOYSA-M choline chloride Chemical compound [Cl-].C[N+](C)(C)CCO SGMZJAMFUVOLNK-UHFFFAOYSA-M 0.000 claims description 9
- 239000001257 hydrogen Chemical group 0.000 claims description 7
- 229910052739 hydrogen Chemical group 0.000 claims description 7
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 6
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 5
- 239000002041 carbon nanotube Substances 0.000 claims description 5
- 239000002131 composite material Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 229910021389 graphene Inorganic materials 0.000 claims description 4
- 235000017166 Bambusa arundinacea Nutrition 0.000 claims description 3
- 235000017491 Bambusa tulda Nutrition 0.000 claims description 3
- 241001330002 Bambuseae Species 0.000 claims description 3
- 235000015334 Phyllostachys viridis Nutrition 0.000 claims description 3
- 150000001408 amides Chemical class 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims description 3
- 239000011425 bamboo Substances 0.000 claims description 3
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 238000002156 mixing Methods 0.000 abstract description 8
- 238000003980 solgel method Methods 0.000 abstract description 6
- 239000000374 eutectic mixture Substances 0.000 abstract 3
- 230000000052 comparative effect Effects 0.000 description 15
- 229910010413 TiO 2 Inorganic materials 0.000 description 14
- 239000004202 carbamide Substances 0.000 description 10
- 230000004048 modification Effects 0.000 description 10
- 238000012986 modification Methods 0.000 description 10
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 10
- 238000002360 preparation method Methods 0.000 description 9
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 8
- 238000001914 filtration Methods 0.000 description 8
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- 239000003153 chemical reaction reagent Substances 0.000 description 6
- 230000002194 synthesizing effect Effects 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 238000009736 wetting Methods 0.000 description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- 238000006482 condensation reaction Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229910044991 metal oxide Inorganic materials 0.000 description 4
- 238000002411 thermogravimetry Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 230000033228 biological regulation Effects 0.000 description 3
- 238000009388 chemical precipitation Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 239000008151 electrolyte solution Substances 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- NJTGANWAUPEOAX-UHFFFAOYSA-N molport-023-220-454 Chemical compound OCC(O)CO.OCC(O)CO NJTGANWAUPEOAX-UHFFFAOYSA-N 0.000 description 3
- 239000002159 nanocrystal Substances 0.000 description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 3
- 239000002033 PVDF binder Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- 230000002427 irreversible effect Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 235000011837 pasties Nutrition 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 230000003245 working effect Effects 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000443 aerosol Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 239000002134 carbon nanofiber Substances 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 238000011175 product filtration Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Classifications
-
- 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
- Y02E60/10—Energy storage using batteries
-
- 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
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
The invention provides a sol-gel method for modifying carbon material for an electrode at low temperature, normal pressure and short time by using a eutectic mixture combined with microwave heating, which comprises the steps of mixing the carbon material with a titanium dioxide precursor, the eutectic mixture, water and an alcohol solvent, carrying out first-stage microwave heating, then adding the same eutectic mixture, water and the alcohol solvent, and carrying out second-stage microwave heating to synthesize the carbon material for the electrode, wherein the carbon material for the electrode contains titanium hydroxide and anatase crystalline phase titanium dioxide which are uniformly distributed and fixed on the carbon material, and can be applied to electrode materials of capacitive desalination, super capacitors or energy storage devices.
Description
[technical field]
Present invention is directed to the method for modifying of electrode carbon material, be particularly to utilize and melt mixed solution altogether and form titanium hydroxide and anatase crystal phase titanium dioxide in conjunction with the sol-gel method of microwave heating and be fixed on method on carbon material.
[background technology]
Material at present based on carbon has been widely used on the fields such as filamentary material, lithium cell, fuel cell, ultracapacitor, capacitive desalination and hydrogen-storing device, conventional carbon material comprises porousness activated carbon powder, carbon nanofiber, carbon aerosol, carbon nanotube, reticulated structure activated carbon etc., and wherein porousness activated carbon is often applied on electrode materials.
But, when activated carbon is applied in electrode materials, the absorption of irreversible physical property can be produced to some compositions in electrolytic solution, and then reduce capacitive energy and the work-ing life of electrode materials, therefore need to carry out modification to activated carbon.One of modification mode of current active carbon material is chemical modification, such as add alkali (as KOH or NaOH), its Main Function is the wetting ability (wettability) of modified activated carbon, activated carbon surface is made to contain polar functional base and increase its surface hydrophilicity, be easy to close to carbon material electrode in order to water system electrolyte solution, but the increase of polar functional base can reduce the electroconductibility of carbon material, be unfavorable for the transfer of electronics in electrode materials, or the Surface Polarization phenomenon of carbon material can be caused, and this modification mode cannot promote wetting ability and the electroconductibility of carbon material simultaneously.
Another kind of modification mode is for adding nano-metal-oxide, use blending (blending), nano-metal-oxide adds or is fixed on active carbon material by the modes such as chemical precipitation method or sol-gel method (sol-gel), remove the polar functional base on carbon material surface, to increase the electroconductibility of carbon material, but this method of modifying easily makes carbon material, and surface becomes hydrophobicity, and blending, chemical precipitation method or sol-gel method have metal oxide skewness, particle is excessive or synthesis step is numerous and diverse, time-consuming, need the problems such as aftertreatment high temperature (200-500 DEG C) sintering, do not meet the ecological requirements of carbon reduction, and this modification mode cannot promote wetting ability and the electroconductibility of carbon material simultaneously.
[summary of the invention]
The invention provides use and melt mixed solution (deepeutecticsolvents altogether; DES) sol-gel method heated in conjunction with microwave (microwave) carries out the method for modification to carbon material, can under the condition of normal pressure of the low temperature of 80 DEG C to 100 DEG C and 1 normal atmosphere (atm), within the short period of time of 30 to 120 minutes, form titanium hydroxide (TiOH) and anatase crystal phase titanium dioxide (anatase-TiO simultaneously
2) react produce bond with carbon material, and the titanium hydroxide formed (TiOH) and anatase crystal phase titanium dioxide are uniformly distributed in surface or the hole inside of carbon material, can increase wetting ability and the electron transmission of carbon material, be a kind ofly meet environmental requirement and the carbon material method of modifying of low cost simultaneously.
Meanwhile, when this carbon modified material is applied to electrode materials, capacitive energy and the work-ing life of electrode materials can be improved, and charge-discharge velocity and the service efficiency of electrode materials can be increased.
According to an embodiment, provide the method for modifying of carbon material, this method comprises: by carbon material and titanium dioxide precursor, melt mixed solution (DES), water and alcoholic solvent altogether and mix, carry out first stage microwave heating, by the first stage product filtration of generation; Add in first stage product again after filtering and aforementionedly melt mixed solution, water and aforementioned alcoholic solvent altogether, carry out subordinate phase microwave heating, synthesize the composite carbon material be fixed on containing titanium hydroxide and anatase crystal phase titanium dioxide on carbon material.
In order to the above-mentioned purpose of the present invention, feature and advantage can be become apparent, below coordinate embodiment, be described in detail below:
[accompanying drawing explanation]
Fig. 1 shows preparation example 1 and uses and different melt mixed solution (DES) adding proportion altogether to synthesizing anatase crystal phase titanium dioxide (anatase-TiO
2) the X-ray diffractometer (XRD) of effectiveness comparison of powder analyzes collection of illustrative plates;
Fig. 2 shows preparation example 2 and uses different microwave heating time to synthesizing anatase crystal phase titanium dioxide (anatase-TiO
2) the X-ray diffractometer (XRD) of effectiveness comparison of powder analyzes collection of illustrative plates;
Fig. 3 shows preparation example 3 to be added and not to melt mixed solution altogether to synthesizing anatase crystal phase titanium dioxide (anatase-TiO with adding
2) the X-ray diffractometer (XRD) of effectiveness comparison of powder analyzes collection of illustrative plates; And
Collection of illustrative plates analyzed by the X-ray diffractometer (XRD) that Fig. 4 shows the modified activated carbon of the unmodified activated carbon of comparative example 1 and embodiment 1-3.
[embodiment]
The enforcement of method of modifying of the present invention can be divided into two stages: (1) first stage is that regulation and control melt the content of mixed solution altogether to suppress titanium dioxide (TiO
2) hydrolysis-condensation reaction (hydrolysis-condensationreaction), control the growing amount of titanium hydroxide (TiOH) by this; (2) subordinate phase is nucleation and crystallization (crystallization) reaction of titanium dioxide, promotes the crystallization of titanium dioxide by this, forms anatase crystal phase titanium dioxide (anatase-TiO
2).
In the step of first stage, first utilize alcoholic solvent to make carbon material be dispersed in solvent, then add again by titanium dioxide precursor, the reagent melting the different ratios that mixed solution (DES) and water are prepared altogether.In one embodiment, the weight ratio of carbon material and alcoholic solvent is about 1:80, and the weight ratio of carbon material and titanium dioxide precursor is about 4:1 to 2:1, and the mol ratio that titanium dioxide precursor melts mixed solution (DES) together can between about 1:0.25 ~ 1:1.5, and the mol ratio of titanium dioxide precursor and water is then between 1:5 ~ 1:30.Under low temperature (less than 100 DEG C) and normal pressure (1atm), carry out the microwave heating of first stage, in one embodiment, the microwave heating time of first stage is about 30 minutes.
In the step of subordinate phase, after the synthetic product of first stage after filtration program, add and melt mixed solution (DES) altogether as aforementioned, the reagent that water and alcoholic solvent are allocated, in one embodiment, the synthetic product of first stage after filtering and the weight ratio of alcoholic solvent are 1:30, the mol ratio of melting mixed solution (DES) and water altogether then can between about between 1:0 ~ 1:18, and the weight ratio that the synthetic product filtering the rear first stage melts mixed solution (DES) is together about 1:3.6, the microwave heating of subordinate phase is carried out under low temperature (less than 100 DEG C) and normal pressure (1atm), in one embodiment, the microwave heating time of subordinate phase is about 60 minutes.
The microwave power of first stage and subordinate phase microwave heating can be 800W, and microwave frequency can be 2.45GHz, and the summation of first stage and subordinate phase microwave heating time can be 30 to 120 minutes.
The mixed solution (DES) that melts altogether used in the present invention is made up of with hydrogen bond supplier quaternary ammonium halide (quaternaryammoniumsalts), and wherein quaternary ammonium halide is such as choline chloride 60 (cholinechloride; ChCl), hydrogen bond supplier comprises polyvalent alcohol (polyalcohols), carboxylic acid (carboxylicacids), amine (amines) or acid amides (amides), be such as urea (urea) or glycerine (glycerol), and the mol ratio that quaternary ammonium halide mixes with hydrogen bond supplier is about 1:1 ~ 1:8, under this proportional range, the melting point of quaternary ammonium halide and hydrogen bond supplier can be down to its eutectic point, presents liquid form mixt.
The carbon material of institute of the present invention modification can be activated carbon (activatedcarbon), bamboo carbon (bamboocharcoal), carbon nanotube (carbonnanotube, CNT) or Graphene (graphene).In addition, activated carbon also can be the form of active carbon cloth (activatedcarboncloth).The specific surface area of carbon material is for being greater than 300m
2/ g, and the hole diameter of carbon material is between 1nm-1000nm.
Alcoholic solvent used in the present invention can be ethanol (ethanol), Virahol (isopropanol; IPA) or butanols (n-butanol), titanium dioxide precursor used in the present invention is such as titanium tetraisopropylate (titaniumtetraisopropoxide; TIP) or four n-butyl titaniums (titaniumbutoxide).
Below enumerate each embodiment and illustrate that the relevant electric characteristics of electrode made by the method for modifying of the carbon material of this announcement and carbon modified material:
[preparation example 1]
Synthesizing anatase crystalline phase titanium dioxide (anatase-TiO
2) the titanium dioxide precursor of powder melts the ratio regulation and control of mixed solution together
Using choline chloride 60 (ChCl) to mix mol ratio with glycerine (Glycerol) is that 1:2 is mixed with and melts mixed solution (DES) altogether, titanium dioxide precursor is titanium tetraisopropylate (TIP), and alcoholic solvent is Virahol (IPA).
With titanium dioxide precursor (TIP): alcoholic solvent (IPA): the mol ratio of water is for 1:3:100, and titanium dioxide precursor (TIP): the mol ratio of melting mixed solution (DES) is altogether respectively 1:0.25,1:0.50,1:0.75,1:1.0,1:1.5, carries out microwave heating 90 minutes under the normal pressure of 80 ~ 85 DEG C and 1atm.
Utilize X-ray diffractometer (X-rayDiffraction; XRD) analyze the synthetic product be prepared from above-mentioned condition, result as shown in Figure 1.Can be learnt by the XRD analysis result of Fig. 1, titanium dioxide precursor (TIP): the mol ratio of melting mixed solution (DES) altogether all can synthesize anatase crystal phase titanium dioxide (anatase-TiO between 1:0.25 ~ 1:1.15
2) nanocrystal.
[preparation example 2]
Synthesizing anatase crystalline phase titanium dioxide (anatase-TiO
2) powder microwave heating time regulation and control
Using choline chloride 60 (ChCl) to mix mol ratio with urea (Urea) is that 1:2 is mixed with and melts mixed solution (DES) altogether, titanium dioxide precursor is titanium tetraisopropylate (TIP), and alcoholic solvent is Virahol (IPA).
With titanium dioxide precursor (TIP): alcoholic solvent (IPA): melt mixed solution (DES) altogether: the mol ratio of water, for 1:3:1:100, carries out microwave heating respectively 30,60,90,120 minutes under the normal pressure of 80 ~ 85 DEG C and 1atm.
Utilize the synthetic product that X-ray diffractometer (XRD) analysis is prepared from above-mentioned microwave heating time condition, result as shown in Figure 2.Can be learnt by the XRD analysis result of Fig. 2, microwave heating time can synthesize anatase crystal phase titanium dioxide (anatase-TiO between 30 to 120 minutes
2) nanocrystal.
[preparation example 3]
Add and melt mixed solution (DES) altogether to synthesis anatase crystal phase titanium dioxide (anatase-TiO
2) effectiveness comparison of powder
Using choline chloride 60 (ChCl) to mix mol ratio with glycerine (Glycerol) is that 1:2 is mixed with the first and melts mixed solution (DES-glycerol) altogether, using choline chloride 60 (ChCl) to mix mol ratio with urea (Urea) is that 1:2 is mixed with the second and melts mixed solution (DES-urea) altogether, titanium dioxide precursor is titanium tetraisopropylate (TIP), and alcoholic solvent is Virahol (IPA).
With titanium dioxide precursor (TIP): alcoholic solvent (IPA): the mol ratio of water is for 1:3:100, and respectively with titanium dioxide precursor (TIP): melt the mol ratio of mixed solution (DES) altogether for 1:0, titanium dioxide precursor (TIP): the first mol ratio of melting mixed solution (DES-glycerol) is altogether 1:1, titanium dioxide precursor (TIP): the mol ratio that the second melts mixed solution (DES-urea) is altogether 1:1, carries out microwave heating 90 minutes respectively under the normal pressure of 80 ~ 85 DEG C and 1atm.
Utilize the synthetic product that X-ray diffractometer (XRD) analysis is prepared from above-mentioned condition, result as shown in Figure 3.Can be learnt by the XRD analysis result of Fig. 3, not add and melt mixed solution altogether and cannot synthesize anatase crystal phase titanium dioxide (anatase-TiO
2), and add the first or the second and melt mixed solution altogether and all can synthesize anatase crystal phase titanium dioxide (anatase-TiO
2), therefore add and melt mixed solution altogether and contribute to low temperature and form anatase crystal phase titanium dioxide fast.
[embodiment 1-3 and comparative example 1]
With comparing of the activated carbon of anatase crystal phase titanium dioxide modification and unmodified activated carbon
Using choline chloride 60 (ChCl) to mix mol ratio with glycerine (Glycerol) is that 1:2 is mixed with and melts mixed solution (DES) altogether, titanium dioxide precursor is titanium tetraisopropylate (TIP), and alcoholic solvent is Virahol (IPA).
First in reaction flask, insert the activated carbon of 2 grams, the Virahol of 200 milliliters (mL) (IPA) is utilized to make activated carbon dispersed, the weight ratio of carbon material and alcoholic solvent is about 1:80, then the mol ratio adding TIP:DES is respectively 1:0.25,1:0.75,1:1, and TIP:H
2the mol ratio of O is TIP, DES and H of 1:15
2three kinds of reagent that O blending ratio is different, under the normal pressure of 80 ~ 85 DEG C and 1atm, carry out the microwave heating 30 minutes of first stage, microwave power is 800W, and frequency is 2.45GHz, is filtered by the synthetic product of the first stage obtained.
Add alcoholic solvent again in the synthetic product of first stage after filtration, the synthetic product of first stage after wherein filtering and the weight ratio of alcoholic solvent are 1:30, add DES:H more afterwards
2the mol ratio of O is the reagent of 1:18, and wherein filter after the synthetic product of first stage and the weight ratio of DES be 1:3.6, the microwave heating 60 minutes of subordinate phase is carried out under the normal pressure of 80 ~ 85 DEG C and 1atm, microwave power is 800W, frequency is 2.45GHz, completes the preparation of the modified activated carbon of embodiment 1-3.
Comparative example 1 is unmodified activated carbon.
X-ray diffractometer (XRD) is utilized to analyze the modified activated carbon AC/TiO of embodiment 1-3
2-TIP:DES=1:0.25, AC/TiO
2-TIP:DES=1:0.75, AC/TiO
2the unmodified activated carbon (AC) of-TIP:DES=1:1 and comparative example 1, result as shown in Figure 4.Can be learnt by the XRD analysis result of Fig. 4, the unmodified activated carbon (AC) of comparative example 1 is that 25.4 ° of places there is no obvious crest in angle (2 θ), the modified activated carbon of embodiment 1-3 then obviously increases in the peak intensity that angle (2 θ) is 25.4 ° of places, and this result represents that the modification of embodiment 1-3 effectively can fix tool anatase crystal phase titanium dioxide (anatase-TiO
2) on activated carbon, and found that by Fig. 4, when the mol ratio of the TIP:DES that modified activated carbon uses is for 1:0.75, its anatase crystal phase titanium dioxide (anatase-TiO
2) Crystal the highest, this result and preparation example 1 synthesizing anatase crystalline phase titanium dioxide (anatase-TiO
2) result of powder conforms to.
[embodiment 4]
With the activated carbon of anatase crystal phase titanium dioxide modification
Using choline chloride 60 (ChCl) to mix mol ratio with urea (Urea) is that 1:2 is mixed with and melts mixed solution (DES) altogether, titanium dioxide precursor is titanium tetraisopropylate (TIP), and alcoholic solvent is Virahol (IPA).
First in reaction flask, insert the activated carbon of 2 grams, the Virahol of 200 milliliters (mL) (IPA) is utilized to make activated carbon dispersed, the weight ratio of carbon material and alcoholic solvent is about 1:80, and the mol ratio then adding TIP:DES is 1:1, and TIP:H
2the mol ratio of O is TIP, DES and H of 1:15
2the mix reagent of O, under the normal pressure of 80 ~ 85 DEG C and 1atm, carry out the microwave heating 30 minutes of first stage, microwave power is 800W, and frequency is 2.45GHz, and the synthetic product of the first stage obtained is carried out filter.
Add alcoholic solvent again in first stage synthetic product after filtration, the first stage synthetic product after filtration and the weight ratio of alcoholic solvent are 1:30, add DES:H more afterwards
2the mol ratio of O is the reagent of 1:18, and first stage synthetic product after filtering and the weight ratio of DES are 1:3.6, the microwave heating 60 minutes of subordinate phase is carried out under the normal pressure of 80 ~ 85 DEG C and 1atm, microwave power is 800W, frequency is 2.45GHz, completes the preparation of the modified activated carbon of embodiment 4.
[embodiment 5-7 and comparative example 2]
Electrode is made with embodiment 1 and the anatase crystal phase titanium dioxide modified activated carbon of embodiment 3-4 and the unmodified activated carbon of comparative example 1, the capacitance characteristic of column electrode of going forward side by side compares, and wherein the mol ratio of TIP:DES that uses of the modified activated carbon of embodiment 3-4 is for 1:1 and TIP:H
2the mol ratio of O is 1:15.
Electrode fabrication program aspect, by embodiment 1 and the modified activated carbon of embodiment 3-4 and the unmodified activated carbon of comparative example 1, respectively with poly(vinylidene fluoride) (polyvinylidenefluoride; PVDF, molecular weight 534k, solid content 5wt%) and graphite powder (particle diameter 2.7 μm) mixing, wherein modified activated carbon or unmodified activated carbon: poly-difluoroethylene: the weight ratio of graphite powder is 80:10:10, by N-Methyl pyrrolidone (N-methyl-2-pyrrolidone; NMP) solvent adds uniform stirring in said mixture and becomes pasty slurry, coating machine is used to be uniformly coated on the titanium foil of thickness 50 μm with 200 μm of scrapers by pasty slurry, send in 130 DEG C of baking ovens and dry 2 hours, complete the making of the electrode of embodiment 5-7 and comparative example 2, wherein the electrode of embodiment 5-7 is made up of the modified activated carbon of embodiment 1, embodiment 3-4 respectively, and the electrode of comparative example 2 is then made up of the unmodified activated carbon of comparative example 1.
Measure resistivity (bulkresistivity, μ Ω .cm) and ratio capacitance value (specificcapacitance, the F.g of the electrode (being made up of the modified activated carbon of embodiment 3-4) of embodiment 6-7 and the electrode of comparative example 2
-1), result is as shown in table 1.
In addition, with thermogravimeter (thermogravimetricanalyzer; TGA) modified activated carbon of embodiment 3-4 is detected, 800 DEG C are warming up to from 30 DEG C under oxygen with the heat-up rate of per minute 20 DEG C, can be calculated in the modified activated carbon of embodiment 3-4 by TGA analytical results, be fixed on the anatase crystal phase titanium dioxide (anatase-TiO on activated carbon
2) content (weight percent, wt%), result is as shown in table 1.
The modified activated carbon of table 1. embodiment 3-4 and the unmodified activated carbon of comparative example 1 and the electrode characteristic be prepared from thereof
The result of table 1 shows via the anatase crystal phase titanium dioxide (anatase-TiO contained by the modified activated carbon of the embodiment 3-4 prepared by the application's method of modifying
2) content be respectively 7.18% and 5.99%.
In addition, the resistance value compared to the electrode prepared by the unmodified activated carbon of comparative example 1 is 107.3 μ Ω .cm, and the resistance value of the electrode prepared by the modified activated carbon of embodiment 3-4 can be down to 95.0 μ Ω .cm.
And in capacitive energy, compared to the ratio capacitance value of the electrode prepared by the unmodified activated carbon of comparative example 1, the ratio capacitance value of the electrode prepared by the modified activated carbon of embodiment 3-4 can promote about 1.3 times.
By the result of table 1 is provable can by anatase crystal phase titanium dioxide (anatase-TiO via method of modifying of the present invention
2) be fixed on activated carbon, and when the modified activated carbon prepared by this method of modifying is applied to electrode materials, electroconductibility and the capacitive energy of electrode effectively can be promoted.
In addition, x-ray photoelectron power spectrum (X-rayphotoelectronspectroscopy is carried out to the modified activated carbon of embodiment 1 and embodiment 3, XPS) analyze, and measure the ratio capacitance value of the electrode (electrode of embodiment 5 and embodiment 6) be prepared from by the modified activated carbon of embodiment 1 and embodiment 3, result as listed in table 2.
The XPS analysis of table 2. modified activated carbon and the ratio capacitance value of electrode made thereof
Can be learnt by the result of table 2, utilize the addition changing and melt mixed solution (DES) altogether, can effectively control to form anatase crystal phase titanium dioxide (anatase-TiO
2) hydrolysis-condensation reaction, and then the growing amount of controllable TiOH.When the addition melting mixed solution (DES) altogether increases, anatase crystal phase titanium dioxide (anatase-TiO
2) content there is no too large change, but the growing amount of its TiOH then can increase relatively.The growing amount increase of TiOH can make the hydrated ion in water system electrolyte solution comparatively be easy to close to electrode surface, and then the ratio capacitance value of electrode is increased, as shown in the result of table 2, when the adding proportion of melting mixed solution (DES) altogether increases to 1 by 0.25, then the ratio capacitance value of its electrode made by modified activated carbon be prepared from is also by 46.4F.g
-1be promoted to 53.4F.g
-1.
The application's method of modifying uses and melts mixed solution altogether in conjunction with microwave heating, owing to melting mixed solution Absorbable rod microwave altogether, and there is the function promoting titanium dioxide crystal, therefore contribute to low temperature (less than 100 DEG C), normal pressure (1atm) and in the short period of time (being less than 2 hours), form titanium hydroxide (TiOH) and anatase crystal phase titanium dioxide (anatase-TiO simultaneously
2) nano-crystal grains is fixed on carbon material, therefore can increase electroconductibility and the wetting ability of carbon material simultaneously.
In addition, can learn via analytical results modified activated carbon being carried out to thermogravimetric analysis (TGA) and x-ray photoelectron power spectrum (XPS), weight ratio containing anatase crystal phase titanium dioxide in the composite carbon material made according to the application's method of modifying is about 4-10%, and the weight ratio containing titanium hydroxide is about 15-50%.
In addition, according to the application's method of modifying, the addition melting mixed solution altogether can be utilized to control the hydrolysis-condensation reaction speed of anatase crystal phase titanium dioxide, and then the titanium hydroxide content in the modified composite carbon material of controllable.
Meanwhile, what the application's method of modifying used melts mixed solution altogether for high polarity and non-volatile solvent, and have the advantages such as bioerodible, nontoxicity, making be simple and easy, with low cost, therefore the application's method of modifying is the carbon material method of modifying of green low cost.
This modified composite carbon material can be applicable to the electrode materials of super capacitor, capacitive desalination or energy storage device, reduce the irreversible adsorption phenomenon of electrode material surface and increase electronic conductivity, to promote the ion suction/desorption ability of electrode, and the ion be conducive in aqueous electrolyte is easy near carbon material electrode surface, reach the effectiveness improving electrode capactitance, increase charge-discharge velocity and the service efficiency of electrode.
In addition, compare modes such as using blending (blending), chemical precipitation method or sol-gel method (sol-gel) traditionally nano-metal-oxide is added or is fixed on the mode of activated carbon, the application's method of modifying also can reach and make titanium hydroxide and anatase crystal phase titanium dioxide be uniformly distributed in the effect that carbon material is surperficial or hole is inner, reduces the clustering phenomena that anatase crystal phase titanium dioxide causes because of nanometer.
Although the present invention has disclosed preferred embodiment as above; so itself and be not used to limit the present invention, any those who are familiar with this art, without departing from the spirit and scope of the invention; when doing a little change and retouching, the protection domain of therefore the present invention is as the criterion when defining depending on claims.
Claims (10)
1. an electrode method of modifying for carbon material, comprising:
By carbon material and titanium dioxide precursor, melt mixed solution, water and alcoholic solvent altogether and mix, carry out the microwave heating of first stage, produce first stage product; And in this first stage product, add this again melt mixed solution, water and this alcoholic solvent altogether, carry out the microwave heating of subordinate phase, synthesize the composite carbon material be fixed on containing titanium hydroxide and anatase crystal phase titanium dioxide on this carbon material,
Wherein the microwave heating of this first stage and this subordinate phase is carried out under temperature is 80-100 DEG C and 1 atmospheric normal pressure, microwave power is 800W, microwave frequency is 2.45GHz, and microwave heating time summation is 30 to 120 minutes, the weight ratio of this carbon material and this titanium dioxide precursor is 4:1 to 2:1, and in this first stage, this titanium dioxide precursor and this mol ratio of melting the addition of mixed solution are altogether 1:0.25 ~ 1:1.5.
2. the electrode as claimed in claim 1 method of modifying of carbon material, wherein this melts mixed solution altogether and is made up of quaternary ammonium halide and hydrogen bond supplier, and the mol ratio that this quaternary ammonium halide mixes with this hydrogen bond supplier is 1:1 ~ 1:8.
3. the electrode as claimed in claim 2 method of modifying of carbon material, wherein this quaternary ammonium halide comprises choline chloride 60, and this hydrogen bond supplier comprises polyvalent alcohol, carboxylic acid, amine or acid amides.
4. the electrode as claimed in claim 1 method of modifying of carbon material, wherein in this subordinate phase, this mol ratio of melting the addition of mixed solution and water is altogether 1:18, and the weight ratio of this first stage product and this alcoholic solvent is 1:30.
5. the electrode as claimed in claim 1 method of modifying of carbon material, wherein this carbon material comprises activated carbon, bamboo carbon, carbon nanotube or Graphene, and the specific surface area of this carbon material is greater than 300m
2/ g, the hole mean diameter of this carbon material is 1nm-1000nm.
6. the electrode as claimed in claim 1 method of modifying of carbon material, wherein this alcoholic solvent comprises ethanol (ethanol), Virahol (isopropanol) or butanols (n-butanol).
7. the electrode as claimed in claim 1 method of modifying of carbon material, wherein this titanium dioxide precursor comprises titanium tetraisopropylate (titaniumtetraisopropoxide) or four n-butyl titaniums (titaniumbutoxide).
8. an electrode carbon material, be made up of the method for modifying of electrode carbon material according to claim 1, be fixed on carbon material containing titanium hydroxide and anatase crystal phase titanium dioxide, the weight ratio of its this anatase crystal phase titanium dioxide contained is 4-10%, and the weight ratio of this titanium hydroxide contained is 15-50%.
9. electrode carbon material as claimed in claim 8, wherein this carbon material comprises activated carbon, bamboo carbon, carbon nanotube or Graphene, and the specific surface area of this carbon material is greater than 300m
2/ g, the hole mean diameter of this carbon material is 1nm-1000nm.
10. electrode carbon material as claimed in claim 8, it is the electrode materials for super capacitor, capacitive desalination or energy storage device.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| TW101149247A TWI487661B (en) | 2012-12-22 | 2012-12-22 | Method of modifying carbon-based electrode material and carbon-based electrode material formed thereby |
| TW101149247 | 2012-12-22 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103879983A CN103879983A (en) | 2014-06-25 |
| CN103879983B true CN103879983B (en) | 2016-01-06 |
Family
ID=50949161
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210585459.3A Active CN103879983B (en) | 2012-12-22 | 2012-12-28 | Method for modifying carbon material for electrode and carbon material for electrode produced by same |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN103879983B (en) |
| TW (1) | TWI487661B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI547444B (en) | 2013-12-19 | 2016-09-01 | 財團法人工業技術研究院 | Electrode for electrochemical removal of phosphorus and apparatus, and method using the electrode |
| US10301199B2 (en) | 2013-12-19 | 2019-05-28 | Industrial Technology Research Institute | Method for selective electrochemical removal of ions in water/wastewater |
| CN104062337B (en) * | 2014-06-17 | 2016-10-05 | 广州科城环保科技有限公司 | A kind of graphite electrode and the method measuring chloride ion content in copper sulphate thereof |
| CN109103029B (en) * | 2018-08-27 | 2020-12-11 | 四川理工学院 | Spiral nano carbon fiber/TiO2Composite material and use thereof |
| CN109768218A (en) * | 2019-03-04 | 2019-05-17 | 浙江众泰汽车制造有限公司 | A kind of hard carbon lithium ion battery negative material of N doping and preparation method thereof and anode plate for lithium ionic cell and lithium ion battery |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006092952A (en) * | 2004-09-24 | 2006-04-06 | Hiroshima Univ | Membrane/electrode assembly, its manufacturing method, and fuel cell using it |
| CN101187646A (en) * | 2007-11-23 | 2008-05-28 | 东华大学 | Granule electrode possessing photoelectric catalytic function and its uses |
| CN102222573A (en) * | 2011-03-25 | 2011-10-19 | 华中科技大学 | Method for preparing titanium dioxide nanocrystalline electrode |
| CN102324505A (en) * | 2011-07-27 | 2012-01-18 | 天津大学 | Preparation method of graphene loaded with anatase type nano titanium dioxide and application thereof |
| CN102666390A (en) * | 2009-11-05 | 2012-09-12 | 新加坡国立大学 | Crystalline mesoporous titanium dioxide and the use thereof in electrochemical devices |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TW201039482A (en) * | 2009-04-27 | 2010-11-01 | Nat Univ Tsing Hua | Preparation of a nanocomposite photoanode for dye-sensitized solar cells |
| CN102509621B (en) * | 2011-10-27 | 2013-10-30 | 中国矿业大学 | Method for preparing flexible-substrate solar cell photoelectrode at low temperature |
-
2012
- 2012-12-22 TW TW101149247A patent/TWI487661B/en active
- 2012-12-28 CN CN201210585459.3A patent/CN103879983B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006092952A (en) * | 2004-09-24 | 2006-04-06 | Hiroshima Univ | Membrane/electrode assembly, its manufacturing method, and fuel cell using it |
| CN101187646A (en) * | 2007-11-23 | 2008-05-28 | 东华大学 | Granule electrode possessing photoelectric catalytic function and its uses |
| CN102666390A (en) * | 2009-11-05 | 2012-09-12 | 新加坡国立大学 | Crystalline mesoporous titanium dioxide and the use thereof in electrochemical devices |
| CN102222573A (en) * | 2011-03-25 | 2011-10-19 | 华中科技大学 | Method for preparing titanium dioxide nanocrystalline electrode |
| CN102324505A (en) * | 2011-07-27 | 2012-01-18 | 天津大学 | Preparation method of graphene loaded with anatase type nano titanium dioxide and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| Deep-Eutectic-Solvent-Assisted Synthesis of Hierarchical Carbon Electrodes Exhibiting Capacitance Retention at High Current Densities;Maria C.Gutierrez et al.;《Chemistry-A European Journal》;20110817;第17卷;10533-10537 * |
Also Published As
| Publication number | Publication date |
|---|---|
| TWI487661B (en) | 2015-06-11 |
| TW201425215A (en) | 2014-07-01 |
| CN103879983A (en) | 2014-06-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6843129B2 (en) | High nickel positive electrode material for lithium ion batteries coated with modified superhydrophobic material and its preparation method | |
| CN103879983B (en) | Method for modifying carbon material for electrode and carbon material for electrode produced by same | |
| TWI667299B (en) | Coating liquid, coating film and composite material | |
| Zhang et al. | A strategy for the synthesis of VN@ C and VC@ C core–shell composites with hierarchically porous structures and large specific surface areas for high performance symmetric supercapacitors | |
| Lai et al. | Mesoporous polyaniline or polypyrrole/anatase TiO2 nanocomposite as anode materials for lithium-ion batteries | |
| Kim et al. | Redox deposition of birnessite-type manganese oxide on silicon carbide microspheres for use as supercapacitor electrodes | |
| He et al. | Rapid synthesis of hollow structured MnO2 microspheres and their capacitance | |
| JP5400607B2 (en) | Electrode active material and lithium battery using the same | |
| TW200537726A (en) | Method of forming an electrode structure useful in energy storage devices | |
| Etman et al. | A one-step water based strategy for synthesizing hydrated vanadium pentoxide nanosheets from VO 2 (B) as free-standing electrodes for lithium battery applications | |
| EP2942325B1 (en) | Method for producing metal tin-carbon composites | |
| Yoon et al. | One-pot route for uniform anchoring of TiO2 nanoparticles on reduced graphene oxides and their anode performance for lithium-ion batteries | |
| Lewis et al. | Correlating titania nanostructured morphologies with performance as anode materials for lithium-ion batteries | |
| Venkataramanan et al. | Green synthesis of titania nanowire composites on natural cellulose fibers | |
| CN105047419A (en) | Manganese dioxide/carbon composite electrode material and preparation method thereof, and super capacitor | |
| CN109313989A (en) | Carbon material, capacitor electrode piece and capacitor | |
| CN104300133B (en) | A kind of lithium titanate material of CNT cladding and preparation method thereof | |
| CN105374971A (en) | Li-ion battery diaphragm and preparation method thereof | |
| CN104987715A (en) | Three-dimensional graphene, polyaniline and cobaltosic oxide composite material and preparation method and application | |
| Gopalakrishna et al. | Studies on the influence of weight percentage of multiwalled carbon nanotubes in Mn/Ni/Co nanocomposites for hybrid supercapacitors | |
| Wang et al. | A novel composite for energy storage devices: core–shell MnO 2/polyindole nanotubes supported on reduced graphene oxides | |
| CN106953079B (en) | A kind of multilevel structure carbon nano tube/tin dioxide composite material and preparation method | |
| Juni et al. | Electrochemical characteristics of Cu/Cu2O/C composite electrode for supercapacitor application | |
| CN102906025A (en) | Process for making titanium compounds | |
| KR101815479B1 (en) | Manufacturing method of composite containing crumpled grahphene and cobalt-iron oxide, the composite manufactured thereby and supercapacitor containing the composite |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |