CN106356547B - A kind of cross-linking type polybenzimidazoles/silica high temperature proton exchange film and preparation method thereof with high anti-oxidation ability - Google Patents

A kind of cross-linking type polybenzimidazoles/silica high temperature proton exchange film and preparation method thereof with high anti-oxidation ability Download PDF

Info

Publication number
CN106356547B
CN106356547B CN201610854194.0A CN201610854194A CN106356547B CN 106356547 B CN106356547 B CN 106356547B CN 201610854194 A CN201610854194 A CN 201610854194A CN 106356547 B CN106356547 B CN 106356547B
Authority
CN
China
Prior art keywords
polybenzimidazoles
cross
solution
high temperature
hours
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
Application number
CN201610854194.0A
Other languages
Chinese (zh)
Other versions
CN106356547A (en
Inventor
于书淳
何春霞
杨汉嵩
马晓星
刘会雪
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Zhangjiagang Institute of industrial technology, Dalian Institute of Chemical Physics, China Academy of Sciences
Original Assignee
Zhangjiagang Institute Of Industrial Technology Dalian Institute Of Chemical Physics China Academy Of Sciences
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Zhangjiagang Institute Of Industrial Technology Dalian Institute Of Chemical Physics China Academy Of Sciences filed Critical Zhangjiagang Institute Of Industrial Technology Dalian Institute Of Chemical Physics China Academy Of Sciences
Priority to CN201610854194.0A priority Critical patent/CN106356547B/en
Publication of CN106356547A publication Critical patent/CN106356547A/en
Application granted granted Critical
Publication of CN106356547B publication Critical patent/CN106356547B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/1041—Polymer electrolyte composites, mixtures or blends
    • H01M8/1046—Mixtures of at least one polymer and at least one additive
    • H01M8/1048—Ion-conducting additives, e.g. ion-conducting particles, heteropolyacids, metal phosphate or polybenzimidazole with phosphoric acid
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/1041—Polymer electrolyte composites, mixtures or blends
    • H01M8/1046—Mixtures of at least one polymer and at least one additive
    • H01M8/1051—Non-ion-conducting additives, e.g. stabilisers, SiO2 or ZrO2
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
    • H01M8/1086—After-treatment of the membrane other than by polymerisation
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
    • H01M8/1086—After-treatment of the membrane other than by polymerisation
    • H01M8/1088—Chemical modification, e.g. sulfonation
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M2008/1095—Fuel cells with polymeric electrolytes
    • 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
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Landscapes

  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Sustainable Development (AREA)
  • Sustainable Energy (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Composite Materials (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Fuel Cell (AREA)

Abstract

The invention discloses a kind of cross-linking type polybenzimidazoles/silica high temperature proton exchange film and preparation method thereof with high anti-oxidation ability, the cross linking membrane fills polybenzimidazoles and organosilicon crosslinked resin using the porous polybenzimidazoles containing free radical quencher as substrate in hole.Cross-linking type polybenzimidazoles/silica high temperature proton exchange film proposed by the present invention has preferable Proton conducting ability and excellent oxidation resistance under not humidification conditions, effectively solves the problems, such as the swelling after polybenzimidazoles impregnation of phosphoric acid.Cross-linking type polybenzimidazoles/silica high temperature proton exchange film proposed by the present invention with high anti-oxidation ability can be applied in high temperature proton exchange film fuel cell, direct alcohol fuel cell, electrochemical sensor or other electrochemical appliances use as proton exchange membrane.

Description

A kind of cross-linking type polybenzimidazoles/silica high temperature with high anti-oxidation ability Proton exchange membrane and preparation method thereof
Technical field
The invention belongs to fuel cell material technical fields, and in particular to a kind of cross-linking type with high anti-oxidation ability is poly- Benzimidazole/silica high temperature proton exchange film and preparation method thereof.
Background technique
Proton Exchange Membrane Fuel Cells (PEMFC) is a kind of efficient, cleaning, environmental-friendly power generator, is electronic vapour The ideal power source of vehicle can also be used as the Military Powers or portable power etc. such as dispersion power station, submarine and spacecraft, have very Wide application prospect.However now widely used is perfluor type sulfonic acid membrane cell using Nafion as representative, but The proton conducting ability of this kind of proton exchange membrane is influenced very big by water content in film and temperature, and alcohol-rejecting ability is poor, the work of PEMFC Make temperature no more than 80 DEG C.Since PEMFC is limited by operating temperature, so that it faces CO tolerance in practical application The problems such as difference, the hydro-thermal difficult management of system.Therefore PEMFC running temperature is increased to 100 DEG C or more, it can be efficiently against The above problem of traditional Nafion base PEMFC, the fuel cell (FC) of this type are normally referred to as high temperature proton exchange film combustion Expect battery (HT-PEMFC), is an important developing direction of PEMFC technology.
HT-PEMFC system has the following advantages: 1) electrochemical reaction speed improves, and effectively reduces electrochemical cathode polarization Overpotential allows to reduce catalyst load amount, allow using non-platinum catalyst；2) humidification requirements of reaction gas are reduced；3) electric Pool inner water exists with gas phase simplifies hydro-thermal management；In addition, HT-PEMFC simplifies FC cooling system to a certain extent.In view of HT-PEMFC tempting development prospect has carried out the development of HT-PEMFC critical material extensively both at home and abroad, including high temperature proton is handed over Change film, catalyst and carrier etc., and achieve preferable PRELIMINARY RESULTS, wherein high temperature proton exchange film be research hot spot it One.
The research of HT-PEMFC proton exchange membrane is concentrated mainly on polybenzimidazoles (PBI) at present, it is in 1959 Year is reported for the first time in United States Patent (USP), and Hoechst Celanese company, the U.S. introduces PBI film product to the market within 1988.Such as The present, PBI is as polymer-based material the most outstanding in engineering thermoplasties, in the high temperature proton exchange for being used as HT-PEMFC Huge validity and feasibility are shown in terms of film.But PBI type membrane material (T >=150 DEG C) in hot operation, meeting can not It degrades with avoiding.
The study found that oxygen penetrates into anode-side by film, in anode Pt and micro transition in fuel cell operation Under the catalytic action of metal ion, the free radicals such as OH and HOO are formed, the nitrogen-containing group on OH free radical attack PBI main chain, HOO free radical attacks the C-H bond on phenyl ring, makes PBI backbone breaking；High-temperature oxidation environment is also easy to make on PBI main chain simultaneously Two Amino End Groups oxidation, carboxyl end group occur decarboxylic reaction generate phenylene free radical.These free radicals generated can aggravate PBI The degradation of film, causes battery performance to decline to a great extent.Room Jian Hua etc. is (more using epoxides (CN 200710171866.9), dihalo- Halogen) alkane (CN 200710171865.4) and maleic anhydride (CN 200710171867.3) be to an end ammonia on PBI main chain Base carries out crosslinking protection, to slow down the degradation of film；Li Zhongfang et al. uses urea (101768270 A of CN), as Amino End Group Protectiveness reagent PBI is modified.Variable valency metal type free base quencher (such as CeO2、MnO2Deng) or change polymerization The free radical generated in HT-PEMFC operational process can be effectively quenched in object structure, to slow down the degradation of PBI film.
It is easy the problems such as to be attacked and degraded by free radical in conclusion obtaining such proton exchange membrane polymeric substrates at present Its commercialized application is restricted, by adding free radical quencher in film, constructing cross-linked structure in film, can effectively be kept away Exempt from free radical attack and degrade, promotes the service life of film, and improve the dimensional stability of film.
Summary of the invention
Based on the deficiencies of the prior art, it is poly- that the purpose of the present invention is to provide a kind of cross-linking types with high anti-oxidation ability Benzimidazole/silica high temperature proton exchange film and preparation method thereof, by with the porous polyphenyl containing free radical quencher And imidazoles is substrate, filling polybenzimidazoles and organosilicon crosslinked resin in hole, by impregnation of phosphoric acid, to improve polyphenyl and miaow The antioxygenic property and dimensional stability of azoles.
To achieve the goals above, the technical solution adopted by the present invention are as follows:
A kind of cross-linking type polybenzimidazoles/silica high temperature proton exchange film preparation side with high anti-oxidation ability Method, comprising the following steps:
A kind of cross-linking type polybenzimidazoles/silica high temperature proton exchange film preparation side with high anti-oxidation ability Method, comprising the following steps:
(1) polybenzimidazoles is dissolved in high boiling solvent, adds free radical quencher, ultrasonic disperse is cast Mould liquid；In mold liquid, the additive amount of polybenzimidazoles is the 0.2 ~ 5% of high boiling solvent quality, the additive amount of free radical quencher It is the 0.05 ~ 1.0% of high boiling solvent quality；
(2) by the injection casting film plate of mold liquid obtained by step (1), then it is 25 DEG C ~ 120 that be placed in humidity, which be 20% ~ 95%, temperature, DEG C climatic chamber in 0.2 ~ 12 hour progress gas phase phase transition, be then immersed in 1 in the mixed liquor of high boiling solvent and water ~ It takes out after 5 hours, is dried in vacuo in 25 DEG C ~ 150 DEG C, the perforated inner layer with a thickness of 50 ~ 80 microns is made；
(3) 3- glycidyl ether oxypropyltriethoxysilane and ethyl orthosilicate are added in high boiling solvent, Stirring 10 ~ 60 minutes, obtains organic silicon solution；Polybenzimidazoles is dissolved in high boiling solvent, it is molten to obtain polybenzimidazoles Liquid；Organic silicon solution is stirred and evenly mixed with polybenzimidazoles solution according to mass ratio 1:0.8 ~ 1.2, polybenzimidazoles/have is obtained Machine silicon solution；Wherein, in organic silicon solution 3- glycidyl ether oxypropyltriethoxysilane mass fraction be 5 ~ 30%, The mass fraction of ethyl orthosilicate is 1 ~ 5%, and the mass fraction of polybenzimidazoles is 0.2 ~ 4.8% in polybenzimidazoles solution；
(4) perforated inner layer obtained by step (2) is immersed in polybenzimidazoles/organic silicon solution obtained by step (3), and to Potassium hydroxide is added in polybenzimidazoles/organic silicon solution, is stirred at room temperature 2 ~ 10 hours, cross-linking reaction 2 ~ 24 is small at 30 ~ 100 DEG C When, it is dried in vacuo in 40 ~ 80 DEG C, obtains composite membrane；Wherein, the additional amount of potassium hydroxide is polybenzimidazoles/organic silicon solution 2 ~ 5 times of middle ethyl orthosilicate quality；
(5) composite membrane obtained by step (4) is immersed in phosphoric acid at 80-150 DEG C and is taken out after 10 ~ 48 hours, it is dry, i.e., ?.
Preferably, step (1), high boiling solvent described in (2) (3) are n,N-dimethylacetamide and/or N- methyl pyrrole Pyrrolidone.
Preferably, free radical quencher as described in step (1) is in ceria, manganese dioxide and modified composite powder body One or more, the modified composite powder body is by composite nano-powder by H2PO4 —It modifies and obtains, the nanometer is multiple Closing powder is one or both of silicon dioxide carried ceria and silicon dioxide carried manganese dioxide.
Preferably, the preparation method of modified composite powder body, comprising the following steps: composite nano-powder and phosphate are added In toluene, and flow back 20 ~ 30 hours in 110 ~ 130 DEG C, filter to take filter residue, washing, it is dry to get；
Wherein, the volume ratio of composite nano-powder, phosphate and toluene is 1:0.1 ~ 0.5:25 ~ 50.
Preferably, the preparation method of the composite nano-powder, comprising the following steps: by ceria or manganese dioxide powder Body is added in the aqueous solution of polyvinylpyrrolidone, and ultrasonic disperse is then centrifuged for isolating precipitating, and is added to ethanol water In, after being 10 ~ 12 with ammonium hydroxide adjusting pH, ethyl orthosilicate is added, stirs 8 ~ 12 hours；It is centrifugated out and precipitates, and wash, do It is dry to get；
Wherein, the ethanol water is uniformly mixed so as to obtain by ethyl alcohol and deionized water according to 10 ~ 25:1 of volume ratio；Polyethylene pyrrole The concentration of polyvinylpyrrolidone is 0.015 ~ 0.05 g/mL in the aqueous solution of pyrrolidone, and the additional amount of ethyl orthosilicate is with second The volume metering of alcohol solution, the additional amount of ethyl orthosilicate is 13 ~ 17 mL, polyvinylpyrrolidine in every 1L ethanol water Ketone, ceria or manganese dioxide, ethyl orthosilicate mass ratio be 10 ~ 30:1 ~ 5:14.
Further, the partial size of the free radical quencher is 2 ~ 30 nanometers.
Preferably, the mass fraction of phosphoric acid described in step (5) is 50% ~ 85%.
Cross-linking type polybenzimidazoles/silica the high temperature with high anti-oxidation ability obtained using above-mentioned preparation method Proton exchange membrane.
Wherein, the polybenzimidazoles, high boiling solvent, 3- glycidyl ether oxypropyltriethoxysilane, positive silicon Acetoacetic ester, polyvinylpyrrolidone, phosphate, ceria and manganese dioxide are ordinary commercial products.
The invention has the benefit that
1. the present invention is respectively adopted gas phase phase inversion and prepares perforated inner layer, and will fill polybenzimidazoles in hole and have Machine silicon crosslinked resin, structure of composite membrane obtained is uniform, is suitable for anhydrous system, the high temperature matter that 120 DEG C ~ 200 DEG C of operating temperature Proton exchange film fuel cell.
2. the present invention uses the cross-linked structure of polybenzimidazoles and organosilicon, after film immersion phosphoric acid can be effectively reduced Swelling problem promotes the mechanical strength of composite membrane, while can effectively promote the oxidation resistance of composite membrane.
3. in porous layer prepared by the present invention, the freedom in battery context can be quenched in the free radical quencher of addition Base, to effectively promote the service life of film.
Detailed description of the invention
Fig. 1 is that the polybenzimidazoles of cross-linking type made from embodiment 1/silica high temperature proton exchange film and tradition PBI are multiple Close the swelling ratio curve graph of film；
Fig. 2 be cross-linking type polybenzimidazoles/silica high temperature proton exchange film made from embodiment 1 and embodiment 2 with The inoxidizability curve graph of traditional PBI composite membrane.
Specific embodiment
Polybenzimidazoles (PBI, CAS 25928-81-8) used is purchased from FuMA-Tech company in following example；N- first Base pyrrolidones (NMP, CAS 872-50-4) is purchased from Tianjin great Mao chemical reagents corporation；Ceria (CeO2, CAS 1306-38-3) it is purchased from Beijing Deco Dao Jin Science and Technology Ltd., partial size 5nm；Manganese dioxide (MnO2, CAS 1313-13-9) Purchased from Shanghai Aladdin biochemical technology limited liability company, partial size is 7 nm；3- glycydoxy triethoxysilicane Alkane (KH-561, CAS 2602-34-8) is purchased from Shanghai Mike woods biochemical technology Co., Ltd；Ethyl orthosilicate (TEOS, CAS 78-10-4) purchased from Aladdin is purchased from, content is (with SiO2Meter) it is 28%；Phosphate selects phosphoric acid second diester (CAS 598-02- 7) Shandong Jin Yu chemical industry Co., Ltd, excellent pure grade, are purchased from.
Embodiment 1
A kind of cross-linking type polybenzimidazoles/silica high temperature proton exchange film preparation side with high anti-oxidation ability Method, comprising the following steps:
(1) 5 g PBI are dissolved in 500 g NMP, after stirring 12 hours, filter 2 times to remove impurity；Add 5 g CeO2, it is 30 minutes ultrasonic, obtain mold liquid；
(2) by the injection casting film plate of mold liquid obtained by step (1), then being placed in humidity be 55%(humidification degree), temperature be 80 DEG C Climatic chamber in 6 hours progress gas phase phase transition, be then immersed in NMP aqueous solution and taken out after 1 hour, it is true in 100 DEG C Sky is 10 hours dry, and the perforated inner layer with a thickness of 60 microns is made；Wherein, NMP aqueous solution by NMP and deionized water by volume 1:1 is mixed and is obtained；
(3) 0.5 g PBI is dissolved in 10 g NMP, after stirring 12 hours, filters 2 times to remove impurity, obtain PBI Solution；0.5 g KH-561 and 0.1 g TEOS are added into 9.4 g NMP, stirred 30 minutes, PBI solution, stirring is added 60 minutes, obtain PBI/ organic silicon solution；
(4) perforated inner layer obtained by step (2) is immersed in PBI/ organic silicon solution obtained by step (3), and had to PBI/ 0.5 g potassium hydroxide (KOH) is added in machine silicon solution, is stirred at room temperature at 5 hours, 30 DEG C and stirs 5 hours sufficiently to crosslink Reaction is dried in vacuo in 40 DEG C, obtains composite membrane；
(5) composite membrane obtained by step (4) is immersed in the phosphoric acid of 85 wt% after 24 hours at 60 DEG C and is taken out, 60 DEG C dry Dry 48 hours to get.
In order to be compared with cross-linking type polybenzimidazoles/silica high temperature proton exchange film obtained above, use Solution casting method prepares the PBI film with a thickness of 50 microns, then impregnation of phosphoric acid, and PBI/ phosphoric acid film, specific preparation step is made are as follows: will The nmp solution of PBI is poured in glass mold, is dried in vacuo 25 hours at 80 DEG C, is obtained PBI film；PBI film is immersed in 60 DEG C Phosphoric acid in 60 hours, take out simultaneously 80 DEG C dry 24 hours to get being denoted as traditional PBI composite membrane；Wherein, the NMP of PBI is molten The mass fraction of PBI is 2% in liquid, and the concentration of phosphoric acid is 70 wt%.
The polybenzimidazoles of cross-linking type made from embodiment 1/silica high temperature proton exchange film and tradition PBI composite membrane, Swelling variation under test test different temperatures, as shown in Figure 1.
It will be seen from figure 1 that the polybenzimidazoles of cross-linking type made from embodiment 1/silica high temperature proton exchange film phase Than traditional PBI composite membrane, swelling ratio is decreased obviously at different temperatures, after illustrating the present invention for alleviating PBI impregnation of phosphoric acid Swelling problem has remarkable result.
Embodiment 2
A kind of cross-linking type polybenzimidazoles/silica high temperature proton exchange film preparation side with high anti-oxidation ability Method, comprising the following steps:
(1) 3 g PBI are dissolved in 100 g NMP, after stirring 12 hours, filter 2 times to remove impurity；It adds 0.5 g MnO2, it is 30 minutes ultrasonic, obtain mold liquid；
(2) by the injection casting film plate of mold liquid obtained by step (1), then being placed in humidity be 65%(humidification degree), temperature be 70 DEG C Climatic chamber in 8 hours progress gas phase phase transition, be then immersed in NMP aqueous solution and taken out after 2 hours, it is true in 100 DEG C Sky is 10 hours dry, and the perforated inner layer with a thickness of 70 microns is made；Wherein, NMP aqueous solution by NMP and deionized water by volume 1:1 is mixed and is obtained；
(3) 0.3 g PBI is dissolved in 10 g NMP, after stirring 12 hours, filters 2 times to remove impurity, obtain PBI Solution；1 g KH-561 and 0.3 g TEOS are added into 10 g NMP, stirred 30 minutes, PBI solution is added, stirs 60 points Clock obtains PBI/ organic silicon solution；
(4) perforated inner layer obtained by step (2) is immersed in PBI/ organic silicon solution obtained by step (3), and had to PBI/ 0.6 g KOH is added in machine silicon solution, is stirred at room temperature 8 hours, 30 DEG C are reacted for stirring 10 hours with crosslinking, in 40 DEG C of vacuum It is dry, obtain composite membrane；
(5) composite membrane obtained by step (4) is immersed in the phosphoric acid of 85 wt% after 10 hours at 60 DEG C and is taken out, 120 DEG C Dry 24 hours to get.
In order to be compared with cross-linking type polybenzimidazoles/silica high temperature proton exchange film obtained above, use Solution casting method prepares the PBI film with a thickness of 60 microns, then impregnation of phosphoric acid, and PBI/ phosphoric acid film, specific preparation step is made are as follows: will The nmp solution of PBI is poured in glass mold, is dried in vacuo 25 hours at 80 DEG C, is obtained PBI film；PBI film is immersed in 60 DEG C Phosphoric acid in 60 hours, take out simultaneously 80 DEG C dry 24 hours to get being denoted as traditional PBI composite membrane；Wherein, the NMP of PBI is molten The mass fraction of PBI is 2% in liquid, and the concentration of phosphoric acid is 70 wt%.
By cross-linking type polybenzimidazoles/silica high temperature proton exchange film and tradition made from embodiment 1 and embodiment 2 PBI composite membrane is immersed in 60 DEG C of Fenton reagent, and the residual mass of film, the i.e. antioxygenic property of film were weighed every 24 hours Test, as a result as shown in Figure 2.Wherein, the H of 3 wt% is contained in Fenton reagent2O2And 4 ppm FeSO4。
Figure it is seen that after impregnating 224 hours, cross-linking type polybenzimidazoles/silica high temperature produced by the present invention Proton exchange membrane mass loss is less than 10%, and tradition PBI composite membrane is more than 40% in internal loss in 140 hours, produced by the present invention Cross-linking type polybenzimidazoles/silica high temperature proton exchange film compares tradition PBI composite membrane, and antioxygenic property is obviously improved, This is because the addition of cross-linked structure and free radical quencher in film, effectively improves the antioxygenic property of film.
Embodiment 3
A kind of cross-linking type polybenzimidazoles/silica high temperature proton exchange film preparation side with high anti-oxidation ability Method, comprising the following steps:
(1) 2 g PBI are dissolved in 1000 g NMP, after stirring 12 hours, filter 2 times to remove impurity；It adds 0.5 g modified composite powder body, ultrasound 30 minutes, obtains mold liquid；
(2) by the injection casting film plate of mold liquid obtained by step (1), then being placed in humidity be 65%(humidification degree), temperature be 70 DEG C Climatic chamber in 0.5 hour progress gas phase phase transition, be then immersed in NMP aqueous solution and taken out after 3 hours, in 100 DEG C The perforated inner layer with a thickness of 80 microns is made in vacuum drying 10 hours；Wherein, NMP aqueous solution presses volume by NMP and deionized water It mixes and obtains than 2:1；
(3) 0.1 g PBI is dissolved in 10 g NMP, after stirring 12 hours, filters 2 times to remove impurity, obtain PBI Solution；1 g KH-561 and 0.3 g TEOS are added into 10 g NMP, stirred 30 minutes, PBI solution is added, stirs 60 points Clock obtains PBI/ organic silicon solution；
(4) perforated inner layer obtained by step (2) is immersed in PBI/ organic silicon solution obtained by step (3), and had to PBI/ 0.9 g KOH is added in machine silicon solution, is stirred at room temperature 2 hours, 30 DEG C are reacted for stirring 2 hours with crosslinking, in 40 DEG C of vacuum It is dry, obtain composite membrane；
(5) composite membrane obtained by step (4) is immersed in the phosphoric acid of 85 wt% after 36 hours at 60 DEG C and is taken out, 120 DEG C Dry 24 hours to get.
In above-mentioned preparation method, step (1) the modified composite powder body passes through H by composite nano-powder2PO4 —Modification and , the composite nano-powder is silicon dioxide carried ceria, and the modified composite powder body is denoted as CeO2/SiO2-H2PO4。
CeO2/SiO2-H2PO4The preparation method comprises the following steps: 2 g PVP are dissolved in the deionized water of 60 mL, ultrasonic disperse 30 minutes, then add 0.3 g CeO2, continue ultrasonic disperse 2 hours, be centrifugated out and precipitate, be added to 100 mL ethyl alcohol Aqueous solution (ethyl alcohol and deionized water are mixed according to volume ratio 25:1 and obtain) in, and with mass fraction for 29% ammonium hydroxide adjusting Then pH=10 of solution are rapidly added 1.5 mL ethyl orthosilicates, stir so that ethyl orthosilicate is fully hydrolyzed 8 hours；Centrifugation Precipitating is isolated, washs 2 times, in 80 DEG C of dryings, obtains CeO2/SiO2；By CeO2/SiO2, phosphoric acid second diester and toluene according to Volume ratio 1:0.5:50 is mixed, and is condensed back 20 hours in 120 DEG C, is filtered to take filter residue, washing, it is dry to get.
The CeO2/SiO2-H2PO4Partial size be 25 nanometers, step (1) use modified composite powder body when, be prepared into from this The CeO arrived2/SiO2-H2PO4In weigh 0.5 g.
The polybenzimidazoles of cross-linking type made from embodiment 3/silica high temperature proton exchange film is immersed in 60 DEG C In Fenton reagent, the residual mass of film, i.e. the antioxygenic property test of film were weighed every 24 hours, wherein Fenton reagent In contain 3 wt% H2O2And 4 ppm FeSO4.After impregnating 224 hours, cross-linking type polybenzimidazoles/silica high temperature proton Exchange membrane mass loss is less than 10%.
Embodiment 4
A kind of cross-linking type polybenzimidazoles/silica high temperature proton exchange film preparation side with high anti-oxidation ability Method, comprising the following steps:
(1) 4 g PBI are dissolved in 100 g NMP, after stirring 12 hours, filter 2 times to remove impurity；It adds 0.8 g modified composite powder body, ultrasound 30 minutes, obtains mold liquid；
(2) by the injection casting film plate of mold liquid obtained by step (1), then being placed in humidity be 65%(humidification degree), temperature be 70 DEG C Climatic chamber in 10 hours progress gas phase phase transition, be then immersed in NMP aqueous solution and taken out after 4 hours, it is true in 100 DEG C Sky is 10 hours dry, and the perforated inner layer with a thickness of 50 microns is made；Wherein, NMP aqueous solution by NMP and deionized water by volume 2:1 is mixed and is obtained；
(3) 0.05 g PBI is dissolved in 10 g NMP, after stirring 12 hours, filters 2 times to remove impurity, obtain PBI solution；3 g KH-561 and 0.2 g TEOS are added into 6.8 g NMP, are stirred 30 minutes, PBI solution, stirring is added 60 minutes, obtain PBI/ organic silicon solution；
(4) perforated inner layer obtained by step (2) is immersed in PBI/ organic silicon solution obtained by step (3), and had to PBI/ 0.6 g KOH is added in machine silicon solution, is stirred at room temperature 10 hours, 30 DEG C are reacted for stirring 15 hours with crosslinking, true in 40 DEG C Sky is dry, obtains composite membrane；
(5) composite membrane obtained by step (4) is immersed in the phosphoric acid of 85 wt% after 40 hours at 60 DEG C and is taken out, 120 DEG C Dry 24 hours to get.
In above-mentioned preparation method, step (1) the modified composite powder body passes through H by composite nano-powder2PO4 —Modification and , the composite nano-powder is silicon dioxide carried manganese dioxide (MnO2/SiO2), which is denoted as MnO2/ SiO2-H2PO4。
MnO2/SiO2-H2PO4The preparation method comprises the following steps: 1 g PVP is dissolved in the deionized water of 60 mL, ultrasonic disperse 30 minutes, then add 0.3 g MnO2, continue ultrasonic disperse 2 hours, be centrifugated out and precipitate, be added to 100 mL ethyl alcohol In aqueous solution (ethyl alcohol and deionized water are mixed according to volume ratio 10:1 and obtained), and it is molten with the ammonium hydroxide adjusting that mass fraction is 29% Then pH=11 of liquid are rapidly added 1.5 mL ethyl orthosilicates, stir so that ethyl orthosilicate is fully hydrolyzed 10 hours；Centrifugation Precipitating is isolated, washs 2 times, in 80 DEG C of dryings, obtains MnO2/SiO2；By MnO2/SiO2, phosphoric acid second diester and toluene according to Volume ratio 1:0.2:25 is mixed, and is condensed back 24 hours in 120 DEG C, is filtered to take filter residue, washing, it is dry to get.
The CeO2/SiO2-H2PO4Partial size be 25 nanometers, step (1) use modified composite powder body when, be prepared into from this The CeO arrived2/SiO2-H2PO4In weigh 0.8 g.
Embodiment 5
A kind of cross-linking type polybenzimidazoles/silica high temperature proton exchange film preparation side with high anti-oxidation ability Method, comprising the following steps:
(1) 5 g PBI are dissolved in 100 g NMP, after stirring 12 hours, filter 2 times to remove impurity；It adds 0.2 g modified composite powder body, ultrasound 30 minutes, obtains mold liquid；
(2) by the injection casting film plate of mold liquid obtained by step (1), then being placed in humidity be 65%(humidification degree), temperature be 70 DEG C Climatic chamber in 12 hours progress gas phase phase transition, be then immersed in NMP aqueous solution and taken out after 5 hours, it is true in 100 DEG C Sky is 10 hours dry, and the perforated inner layer with a thickness of 60 microns is made；Wherein, NMP aqueous solution by NMP and deionized water by volume 3:1 is mixed and is obtained；
(3) 0.3 g PBI is dissolved in 10 g NMP, after stirring 12 hours, filters 2 times to remove impurity, obtain PBI Solution；2 g KH-561 and 0.5 g TEOS are added into 7.5 g NMP, are stirred 30 minutes, PBI solution, stirring 60 is added Minute, obtain PBI/ organic silicon solution；
(4) perforated inner layer obtained by step (2) is immersed in PBI/ organic silicon solution obtained by step (3), and had to PBI/ 1 g KOH is added in machine silicon solution, is stirred at room temperature 5 hours, 30 DEG C are reacted for stirring 24 hours with crosslinking, dry in 40 DEG C of vacuum It is dry, obtain composite membrane；
(5) composite membrane obtained by step (4) is immersed in the phosphoric acid of 85 wt% after 48 hours at 60 DEG C and is taken out, 120 DEG C Dry 24 hours to get.
In above-mentioned preparation method, step (1) the modified composite powder body passes through H by composite nano-powder2PO4 —Modification and , the composite nano-powder is silicon dioxide carried ceria, and the modified composite powder body is denoted as CeO2/SiO2-H2PO4。
CeO2/SiO2-H2PO4The preparation method comprises the following steps: 1.8 g PVP are dissolved in the deionized water of 60 mL, ultrasound point It dissipates 30 minutes, then adds 0.3 g CeO2, continue ultrasonic disperse 2 hours, be centrifugated out and precipitate, be added to 100 mL second In alcohol solution (ethyl alcohol and deionized water are mixed according to volume ratio 25:1 and obtained), and the ammonium hydroxide for being 29% with mass fraction is adjusted Then pH=10 of solution are rapidly added 1.4 mL ethyl orthosilicates, stir so that ethyl orthosilicate is fully hydrolyzed 12 hours；From The heart isolates precipitating, washs 2 times, in 80 DEG C of dryings, obtains CeO2/SiO2；By CeO2/SiO2, phosphoric acid second diester and toluene presses Mixed according to volume ratio 1:0.4:45, be condensed back 30 hours in 120 DEG C, filter to take filter residue, washing, it is dry to get.
The CeO2/SiO2-H2PO4Partial size be 25 nanometers, step (1) use modified composite powder body when, be prepared into from this The CeO arrived2/SiO2-H2PO4In weigh 0.2 g.
Cross-linking type polyphenyl and miaow by experimental test, made from embodiment 4 and embodiment 5 with high anti-oxidation ability Azoles/silica high temperature proton exchange film compares tradition PBI composite membrane described in embodiment 1, and antioxygenic property is substantially improved.

Claims (7)

1. a kind of cross-linking type polybenzimidazoles/silica high temperature proton exchange film preparation side with high anti-oxidation ability Method, which comprises the following steps:
(1) polybenzimidazoles is dissolved in high boiling solvent, adds free radical quencher, ultrasonic disperse obtains casting solution； In casting solution, the additive amount of polybenzimidazoles is the 0.2 ~ 5% of high boiling solvent quality, and the additive amount of free radical quencher is height The 0.05 ~ 1.0% of boiling point solvent quality；
(2) by the injection casting film plate of casting solution obtained by step (1), then it is 25 DEG C ~ 120 DEG C that be placed in humidity, which be 20% ~ 95%, temperature, It 0.2 ~ 12 hour in climatic chamber, is then immersed in the aqueous solution of high boiling solvent and is taken out after 1 ~ 5 hour, in 25 DEG C ~ 150 DEG C vacuum drying, is made with a thickness of 50 ~ 80 microns of perforated inner layer；The aqueous solution of the high boiling solvent by high boiling solvent with Deionized water is mixed according to 1 ~ 3:1 of volume ratio and is obtained；
(3) 3- glycidyl ether oxypropyltriethoxysilane and ethyl orthosilicate are added in high boiling solvent, are stirred 10 ~ 60 minutes, obtain organic silicon solution；Polybenzimidazoles is dissolved in high boiling solvent, polybenzimidazoles solution is obtained；It will Organic silicon solution is stirred and evenly mixed with polybenzimidazoles solution according to mass ratio 1:0.8 ~ 1.2, and it is molten to obtain polybenzimidazoles/organosilicon Liquid；Wherein, the mass fraction of 3- glycidyl ether oxypropyltriethoxysilane is 5 ~ 30%, positive silicic acid in organic silicon solution The mass fraction of ethyl ester is 1 ~ 5%, and the mass fraction of polybenzimidazoles is 0.2 ~ 4.8% in polybenzimidazoles solution；
(4) perforated inner layer obtained by step (2) is immersed in polybenzimidazoles/organic silicon solution obtained by step (3), and to polyphenyl And potassium hydroxide is added in imidazoles/organic silicon solution, it is stirred at room temperature at 2 ~ 10 hours, 30 ~ 100 DEG C and stirs 2 ~ 24 hours, in 40 ~ 80 DEG C of vacuum drying, obtain composite membrane；Wherein, the additional amount of potassium hydroxide is positive silicic acid in polybenzimidazoles/organic silicon solution 2 ~ 5 times of ethyl ester quality；
(5) composite membrane obtained by step (4) is immersed in phosphoric acid at 80 ~ 150 DEG C and is taken out after 10 ~ 48 hours, in 60 ~ 120 DEG C It is dry to get；
Step (1), (2), high boiling solvent described in (3) are n,N-dimethylacetamide and/or N-Methyl pyrrolidone.
2. the cross-linking type polybenzimidazoles with high anti-oxidation ability/silica high temperature proton according to claim 1 The preparation method of exchange membrane, it is characterised in that: free radical quencher as described in step (1) be ceria, manganese dioxide and One or more of modified composite powder body, the modified composite powder body are by composite nano-powder by H2PO4 —Modification And obtain, the composite nano-powder be one of silicon dioxide carried ceria and silicon dioxide carried manganese dioxide or Two kinds.
3. the cross-linking type polybenzimidazoles with high anti-oxidation ability/silica high temperature proton according to claim 2 The preparation method of exchange membrane, which is characterized in that the preparation method of modified composite powder body, comprising the following steps: by nano composite powder Body and phosphate are added in toluene, and flow back 20 ~ 30 hours in 110 ~ 130 DEG C, filter to take filter residue, washing, it is dry to get；
Wherein, the volume ratio of composite nano-powder, phosphate and toluene is 1:0.1 ~ 0.5:25 ~ 50.
4. the cross-linking type polybenzimidazoles with high anti-oxidation ability/silica high temperature proton according to claim 2 The preparation method of exchange membrane, which is characterized in that the preparation method of the composite nano-powder, comprising the following steps: by titanium dioxide Cerium or manganese dioxide powder are added in the aqueous solution of polyvinylpyrrolidone, ultrasonic disperse, are then centrifuged for isolating precipitating, and add Enter into ethanol water, after being 10 ~ 12 with ammonium hydroxide adjusting pH, ethyl orthosilicate is added, stirs 8 ~ 12 hours；It is centrifugated out Precipitating, and wash, dry to get；
Wherein, the ethanol water is uniformly mixed so as to obtain by ethyl alcohol and deionized water according to 10 ~ 25:1 of volume ratio；Polyvinylpyrrolidine The concentration of polyvinylpyrrolidone is 0.015 ~ 0.05 g/mL in the aqueous solution of ketone, and the additional amount of ethyl orthosilicate is with ethanol water The volume metering of solution, the additional amount of ethyl orthosilicate is 13 ~ 17 mL, polyvinylpyrrolidone, two in every 1L ethanol water The mass ratio of cerium oxide or manganese dioxide, ethyl orthosilicate is 10 ~ 30:1 ~ 5:14.
5. the cross-linking type polybenzimidazoles with high anti-oxidation ability/silica high temperature proton according to claim 2 The preparation method of exchange membrane, it is characterised in that: the partial size of the free radical quencher is 2 ~ 30 nanometers.
6. the cross-linking type polybenzimidazoles with high anti-oxidation ability/silica high temperature proton according to claim 1 The preparation method of exchange membrane, it is characterised in that: the mass fraction of phosphoric acid described in step (5) is 50% ~ 85%.
7. the cross-linking type polyphenyl with high anti-oxidation ability for using any preparation method of claim 1 to 6 to obtain is simultaneously Imidazoles/silica high temperature proton exchange film.
CN201610854194.0A 2016-09-27 2016-09-27 A kind of cross-linking type polybenzimidazoles/silica high temperature proton exchange film and preparation method thereof with high anti-oxidation ability Active CN106356547B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201610854194.0A CN106356547B (en) 2016-09-27 2016-09-27 A kind of cross-linking type polybenzimidazoles/silica high temperature proton exchange film and preparation method thereof with high anti-oxidation ability

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201610854194.0A CN106356547B (en) 2016-09-27 2016-09-27 A kind of cross-linking type polybenzimidazoles/silica high temperature proton exchange film and preparation method thereof with high anti-oxidation ability

Publications (2)

Publication Number Publication Date
CN106356547A CN106356547A (en) 2017-01-25
CN106356547B true CN106356547B (en) 2019-07-05

Family

ID=57859967

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201610854194.0A Active CN106356547B (en) 2016-09-27 2016-09-27 A kind of cross-linking type polybenzimidazoles/silica high temperature proton exchange film and preparation method thereof with high anti-oxidation ability

Country Status (1)

Country Link
CN (1) CN106356547B (en)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108281690B (en) * 2018-01-30 2020-03-13 温州市赢创新材料技术有限公司 Rare earth nano silicon dioxide proton membrane and preparation method thereof
CN111244513B (en) * 2018-11-28 2021-04-02 中国科学院大连化学物理研究所 High-temperature fuel cell proton exchange membrane and preparation method and application thereof
US11652227B2 (en) * 2019-03-29 2023-05-16 Hyundai Motor Company Antioxidant for fuel cells and fuel cell comprising the same
CN110048148A (en) * 2019-04-24 2019-07-23 东北大学 Polybenzimidazole polymer porous electrolyte membrane preparation method for flow battery
CN111525169B (en) * 2020-04-30 2023-01-24 深圳市众通新能源汽车科技有限公司 Preparation method of high-temperature proton exchange membrane
CN115594847B (en) * 2022-09-06 2023-08-22 上海四羿科技有限公司 Polybenzimidazole ion exchange membrane with high oxidation resistance and preparation method and application thereof

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2483015A1 (en) * 2002-04-25 2003-11-06 Pemeas Gmbh Multilayer electrolyte membrane
CN1253952C (en) * 2004-11-15 2006-04-26 武汉理工大学 Method for producing multi-layer nano composite proton exchange membrane with self-humidifying function
CN100565994C (en) * 2007-12-20 2009-12-02 成都中科来方能源科技有限公司 High temperature proton exchange film for fuel cell and preparation method thereof
CN101735591B (en) * 2009-11-20 2011-08-10 清华大学 Organic-inorganic hybrid cross-linked sulfonated polyaryletherketone polymer electrolyte material and preparation method thereof
CN103887536A (en) * 2014-03-13 2014-06-25 清华大学 Method for preparing polybenzimidazole proton exchange membrane subjected to inorganic material hybridization
CN105601968B (en) * 2015-11-19 2018-09-21 黄河科技学院 A kind of preparation method of polybenzimidazoles multilayer complex films used for high-temperature fuel cell

Also Published As

Publication number Publication date
CN106356547A (en) 2017-01-25

Similar Documents

Publication Publication Date Title
CN106356547B (en) A kind of cross-linking type polybenzimidazoles/silica high temperature proton exchange film and preparation method thereof with high anti-oxidation ability
JP5451892B2 (en) Application of Aromatic Polymer Ion Exchange Membrane and Its Composite Membrane to Acidic Electrolyte Flow Energy Storage Battery
CN111244513B (en) High-temperature fuel cell proton exchange membrane and preparation method and application thereof
CN102468494B (en) A kind of vanadium redox flow battery electrode and preparation method thereof, and all-vanadium flow battery
CN106558719A (en) A kind of polybenzimidazoles with high antioxygenic property/polyvinylbenzylchloride cross-linking type high temperature proton exchange film and preparation method thereof
CN106750441A (en) A kind of poly- triazole ionic liquid of cross-linking type/polybenzimidazoles high temperature proton exchange film and preparation method thereof
CN106549171B (en) A kind of cross-linking type polybenzimidazoles high temperature proton exchange film and preparation method thereof with the high conductivity of high antioxygenic property
CN106750442A (en) A kind of cross-linking type polybenzimidazoles with high conductivity/polyethylene triazole high temperature proton exchange film and preparation method thereof
CN106450392A (en) High conductivity cross-linked organic phosphate polybenzoimidazole high temperature proton exchange membrane and preparation method thereof
CN110041552B (en) Composite high-temperature proton exchange membrane based on sulfonated aryl ether type polybenzimidazole and sulfonated polysilsesquioxane and preparation method thereof
CN101440167B (en) Preparation of SiO2/organic polymer composite proton exchange membrane
CN107221692B (en) A kind of polybenzimidazoles with high anti-oxidation ability/phosphoric acid MULTILAYER COMPOSITE high temperature proton exchange film and preparation method thereof
CN100580013C (en) Preparation method of sulfonated poly(arylether ketone) compound membrane
CN106410247A (en) Polybenzimidazole phosphoric acid high-temperature proton exchange membrane with high phosphoric acid adsorbing capability and preparation method thereof
Yuan et al. Study of poly (organic palygorskite‐methyl methacrylate)/poly (ethylene oxide) blended gel polymer electrolyte for lithium‐ion batteries
CN107221693A (en) A kind of high temperature proton exchange film of polybenzimidazoles/ionic liquid MULTILAYER COMPOSITE and preparation method thereof
Aparicio et al. Hybrid organic-inorganic nanostructured membranes for high temperature proton exchange membranes fuel cells (PEMFC)
CN103700873A (en) Inorganic nanoparticle in-situ modified polybenzimidazole derivative proton exchange membrane and preparation method thereof
CN102623734B (en) Preparation method of high-performance composite proton exchange membrane of fuel cell
CN108102124A (en) Preparation method of modified epoxy silane fuel cell proton exchange membrane
CN111048813B (en) Organic-inorganic composite membrane for iron-chromium flow battery and preparation method thereof
Cheng et al. Polydopamine‐assisted in situ formation of dense aramid nanofibers layer on polyethylene separator for lithium‐ion battery
JP2022553774A (en) anionic polyelectrolytes
Al-Othman et al. Proton Conductivity Studies on Covalent Organic Frameworks (COFs) for The Application of High-Temperature Fuel Cells
Talukdar et al. Polyacrylamide/Nafion® semi-interpenetrating networks as proton-conducting membrane of direct methanol fuel cell

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
TA01 Transfer of patent application right

Effective date of registration: 20190604

Address after: Room 207, Building A, Emerging Industry Development Center, Zhangjiagang Free Trade Zone, Suzhou City, Jiangsu Province

Applicant after: Zhangjiagang Institute of industrial technology, Dalian Institute of Chemical Physics, China Academy of Sciences

Address before: 450005 No. 94 Hanghai Middle Road, Erqi District, Zhengzhou City, Henan Province

Applicant before: Huanghe S & T College

TA01 Transfer of patent application right
GR01 Patent grant
GR01 Patent grant