CN110416582A - A kind of amberplex and preparation method thereof with insulated high-strength non-reaction zone - Google Patents

A kind of amberplex and preparation method thereof with insulated high-strength non-reaction zone Download PDF

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Publication number
CN110416582A
CN110416582A CN201810384926.3A CN201810384926A CN110416582A CN 110416582 A CN110416582 A CN 110416582A CN 201810384926 A CN201810384926 A CN 201810384926A CN 110416582 A CN110416582 A CN 110416582A
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Prior art keywords
amberplex
reaction zone
epoxy resin
strength
insulated high
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CN110416582B (en
Inventor
马相坤
张华民
盛伟
王友
刘盛林
倪泓
陈宁
高涛
南明君
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Dalian Raycom Energy Storage Equipment Co Ltd
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Dalian Raycom Energy Storage Equipment Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • 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
    • 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
    • H01M8/18—Regenerative fuel cells, e.g. redox flow batteries or secondary fuel cells
    • H01M8/184—Regeneration by electrochemical means
    • H01M8/188—Regeneration by electrochemical means by recharging of redox couples containing fluids; Redox flow type 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
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • General Chemical & Material Sciences (AREA)
  • Sustainable Energy (AREA)
  • Sustainable Development (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Composite Materials (AREA)
  • Nanotechnology (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Materials Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Fuel Cell (AREA)
  • Paints Or Removers (AREA)

Abstract

The present invention relates to energy-storage battery fields, especially a kind of amberplex and preparation method thereof with insulated high-strength non-reaction zone, the present invention bad problem of short, bad mechanical strength, insulating properties for all-vanadium flow battery amberplex service life, a kind of effective amberplex non-reaction zone improved method is provided, make the region insulation without ion exchange by coating insualtion resin composition in non-reaction zone, self discharge is reduced, and increases substantially the mechanical strength in the region.Meanwhile the present invention, by carrying out automatic coating to amberplex non-reaction zone, quick air drying makes amberplex generally improve technique and realizes automation, saves artificial and production cost.Relative to traditional ultrasonic welding and hot melt film hot melt integration protection, amberplex non-reaction zone surface coating machine intensity raising of the invention is become apparent from, and can accomplish completely insulated, also more can be resistant to the erosion of strong acid strong oxidizing property electrolyte.It has a good application prospect.

Description

A kind of amberplex and preparation method thereof with insulated high-strength non-reaction zone
Technical field
The present invention relates to energy-storage battery fields, relate more specifically to all-vanadium flow battery field, and in particular to a kind of ion The improved method of exchange membrane non-reaction zone.
Background technique
All-vanadium flow battery is a kind of novel extensive energy-storage battery, and, power height independent with capacity, the service life is long and easily grasps The advantages that making.Amberplex is one of flow battery critical component, its performance directly affects performance and the longevity of flow battery Life.
The major function of amberplex for flow battery includes three aspects: 1, it is molten to separate battery plus-negative plate electrolyte Liquid avoids internal short-circuit of battery；2, the proton or ion channels of inside battery are constructed, galvanic circle is formed；3, selective Allow proton or specific ion to pass through, does not allow active material to pass through, prevent the active matter in battery plus-negative plate electrolyte solution The mutual of matter mixes.Battery ions exchange membrane is better to the selective penetrated property of specific ion or proton, and the coulombic efficiency of battery is higher.By This is as it can be seen that flow battery amberplex should meet following condition:
1) proton of flow battery amberplex or ionic conductivity directly affect the voltage efficiency of battery, diaphragm Proton or ionic conduction selectively directly affect the coulombic efficiency of battery and the capacity stability of battery.Generally for acidic electrolysis Matter solution, it is desirable that amberplex has excellent proton-conducting and selectivity, as the solvent of all-vanadium flow battery is usually Aqueous sulfuric acid, transmitting medium are proton (H+).It is required that amberplex non-conducting energy storage active substance, to improve the library of battery The capacity holding capacity of logical sequence efficiency and battery, reduces the self discharge of battery.
2) flow battery is usually in the harshnesses such as Strong oxdiative reproducibility, acidity or alkalinity, high operating potential, higher temperature Under conditions of run, it is desirable that membrane material component and the structure of film remain unchanged in During Process of Long-term Operation, that is, require membrane material to have There are excellent chemistry and electrochemical stability and durability, excellent corrosion resistance.
3) flow battery is commonly used in large-scale energy storage system, and pile is larger, the pressing force and shearing of battery assembly sealing Power is larger, it is desirable that amberplex has good mechanical performance, that is, has good tensile strength and toughness.
In actual conditions, there are a small amount of ion exchange, this phenomenons will lead to the area for amberplex non-reaction zone two sides Domain precipitates crystal abrasion amberplex, and there is also broken for ionic membrane under the prolonged pressing force in non-reaction zone, shearing force The risk of damage.However how ion is improved there is no to the effective improved method in amberplex non-reaction zone in the prior art The mechanical strength and insulating properties of exchange membrane are urgent technical problem to be solved in the field.
Summary of the invention
In order to make up the blank of the prior art, the present invention provide a kind of insulated high-strength amberplex non-reaction zone and its Preparation method is sprayed using chemical/physical, amberplex non-reaction zone is applied and is covered with one layer of insulated high-strength coating, pole It is big to improve the amberplex zone machines intensity and chemical stability.
To achieve the above object, the invention adopts the following technical scheme:
A kind of insulated high-strength amberplex non-reaction zone, is coated with insualtion resin composition on the non-reaction zone, The insualtion resin composition includes: 20-65wt% nanometer scale ceramics powder, 35-80wt% epoxy resin composition, 1- 5wt% active dispersing agents and the more first amine curing agents of 2-5wt%.
Wherein, the nanometer scale ceramics powder by partial size 5-50nm AL2O3、SiC、Si3N4, at least two powder in MgO Composition.Preferably, using Al2O3, SiC bi-component proportion nano ceramic powder, wherein Al2O3It is total to account for nanometer scale ceramics powder 25-50wt%, SiC of quality account for the 25-50wt% of nanometer scale ceramics total powder quality
The epoxy resin composition is by bisphenol A type epoxy resin, bisphenol f type epoxy resin, polyphenol type glycidol Two or more group in ether epoxy resin, aliphatic glycidyl ether epoxy resin or glycidyl ester type epoxy resin At, it is preferred that it is formed using mass ratio 1:0.1-1:1 bisphenol A type epoxy resin and aliphatic glycidyl ether epoxy resin Mixture.
The active dispersing agents are polyacrylamide, polyacrylic acid and its sodium salt, in hydroxymethyl cellulose, polyvinyl alcohol It is one or more kinds of.
The polynary amine curing agent mixture is diethylenetriamine, tetra-methylenedimine, diamines butylcyclohexane, methylene Two or more composition in bis cyclohexane amine.Preferably, polynary amine curing agent mixture is by diethylenetriamine, four Asias Methanediamine and di-2-ethylhexylphosphine oxide hexamethylene alkanamine composition, wherein diethylenetriamine accounts for polynary amine curing agent mixture gross mass 20-50wt%, tetra-methylenedimine account for the 20-50wt% of polynary amine curing agent mixture gross mass, di-2-ethylhexylphosphine oxide hexamethylene Amine accounts for the 5-15wt% of polynary amine curing agent mixture gross mass.
The preparation method of above-mentioned insualtion resin composition is claimed in second purpose of the invention, comprising the following steps:
S1. epoxy resin is weighed in proportion, is uniformly mixed, and epoxy resin composition is obtained；
S2. nanometer scale ceramics powder is weighed in proportion to stir evenly when being added in epoxy resin composition；
S3. weighing active dispersing agents are added in step S2 obtained component in proportion, are added while stirring until stirring evenly；
S4. it weighs polynary amine curing agent, is added in step S3 component in proportion, is added while stirring until stirring is equal It is even, obtain insulating resin mixture.
The preparation method of insulated high-strength amberplex non-reaction zone is claimed in third purpose of the present invention, will be above-mentioned Insulating resin mixture obtained by step S4 is added in Full-automatic coating machine, coats to amberplex non-reaction zone, coats Condition are as follows: gas source is nitrogen, gas pressure 0.05-0.5MPa, spray head and amberplex surface distance 0.1-10cm, spray head row Fast 0.1-50cm/s, the amberplex after coating is dry under room temperature, obtains the ion with insulated high-strength non-reaction zone Exchange membrane.
The present invention is when in use in high potential, highly acid, strong oxidizing property for all-vanadium flow battery amberplex The problem for causing short amberplex service life, bad mechanical strength, insulating properties bad in environment provides a kind of effective ion Exchange membrane non-reaction zone improved method hands over the region insulation without ion by coating insualtion resin composition in non-reaction zone It changes, reduces self discharge, and increase substantially the mechanical strength in the region.Meanwhile the present invention passes through to the non-reaction of amberplex Area carries out automatic coating, and quick air drying makes amberplex generally improve technique and realizes automation, saves artificial and be produced into This.Relative to traditional ultrasonic welding and hot melt film hot melt integration protection, amberplex non-reaction zone surface of the invention The raising of coating machine intensity becomes apparent from, and can accomplish completely insulated, also more can be resistant to the erosion of strong acid strong oxidizing property electrolyte.Tool There is good application prospect.
Specific embodiment
The present invention is described in detail below by specific embodiment, but is not limited the scope of the invention.Unless otherwise specified, originally Experimental method used by inventing is conventional method, and experiment equipment used, material, reagent etc. commercially obtain.
Coated conditions shown in premix formulation shown in table 1 and table 2 are respectively adopted in following embodiments.
1 premix formulation of table
2 coated conditions of table
Embodiment
S1. epoxy resin is weighed in proportion, is uniformly mixed, and epoxy resin composition is obtained；
S2. nanometer scale ceramics powder is weighed in proportion to stir evenly when being added in epoxy resin composition；
S3. weighing active dispersing agents are added in step S2 obtained component in proportion, are added while stirring until stirring evenly；
S4. it weighs polynary amine curing agent, is added in step S3 component in proportion, is added while stirring until stirring is equal It is even, obtain insulating resin mixture.
S5. insulating resin mixture obtained by above-mentioned steps S4 is added in Full-automatic coating machine, it is coiled untreated Ion exchange film winding is cut into required pattern, when by Full-automatic coating machine, carries out to amberplex non-reaction zone two-sided Coating, coated conditions are as follows: gas source is nitrogen, gas pressure 0.05-0.5MPa, spray head and amberplex surface distance 0.1- 10cm, spray head scanning frequency 0.1-50cm/s, the amberplex after coating is dry under room temperature, obtains non-anti-with insulated high-strength Answer the amberplex in area.
By control raw material proportioning and coated conditions, the thickness, required of amberplex non-reaction zone coating can control Drying time, mechanical strength and cost, to adapt to the design of the all-vanadium flow battery of different demands.
Each application of mixture formula of 3 embodiment 1-18 of table and coating method
Embodiment Ceramics 1 Ceramics 2 Ceramics 3 Resin 1 Resin 2 Resin 3 Dispersing agent Curing agent Coated conditions
1 620 0 0 319 0 0 42 19 Condition 1
2 525 0 0 413 0 0 37 25 Condition 1
3 410 0 0 0 528 0 30 32 Condition 1
4 325 0 0 0 615 0 24 36 Condition 1
5 260 0 0 0 0 677 19 44 Condition 1
6 220 0 0 0 0 719 11 50 Condition 1
7 0 620 0 0 0 319 42 19 Condition 2
8 0 525 0 0 0 413 37 25 Condition 2
9 0 410 0 0 528 0 30 32 Condition 2
10 0 325 0 0 615 0 24 36 Condition 2
11 0 260 0 677 0 0 19 44 Condition 2
12 0 220 0 719 0 0 11 50 Condition 2
13 0 0 620 319 0 0 42 19 Condition 3
14 0 0 525 413 0 0 37 25 Condition 3
15 0 0 410 0 528 0 30 32 Condition 3
16 0 0 325 0 615 0 24 36 Condition 3
17 0 0 260 0 0 677 19 44 Condition 3
18 0 0 220 0 0 719 11 50 Condition 3
1-18 of the embodiment of the present invention, E.I.Du Pont Company are produced into all-vanadium flow battery amberplex original film NR212 progressive It can test and compare, test result is as shown in table 4.
4 embodiment of table and the comparison of comparative example paintability
Note: comparative example is amberplex original film, without any pretreatment.
The preferable specific embodiment of the above, only the invention, but the protection scope of the invention is not It is confined to this, anyone skilled in the art is in the technical scope that the invention discloses, according to the present invention The technical solution of creation and its inventive concept are subject to equivalent substitution or change, should all cover the invention protection scope it It is interior.

Claims (7)

1. a kind of insulated high-strength amberplex non-reaction zone, which is characterized in that in non-reaction zone coating insulating resin combination Object, the insualtion resin composition include: 20-65wt% nanometer scale ceramics powder, 35-80wt% epoxy resin composition, 1- 5wt% active dispersing agents and the more first amine curing agents of 2-5wt%；
Wherein, the nanometer scale ceramics powder by partial size 5-50nm AL2O3、SiC、Si3N4, at least two powder constituents in MgO；
The epoxy resin composition is by bisphenol A type epoxy resin, bisphenol f type epoxy resin, polyphenol type glycidol ether ring Two or more composition in oxygen resin, aliphatic glycidyl ether epoxy resin or glycidyl ester type epoxy resin；
The active dispersing agents are one of polyacrylamide, polyacrylic acid and its sodium salt, hydroxymethyl cellulose, polyvinyl alcohol Or more than one；
The polynary amine curing agent mixture is that diethylenetriamine, tetra-methylenedimine, diamines butylcyclohexane, methylene are bicyclic Two or more composition in hexane amine.
2. insulated high-strength amberplex according to claim 1 non-reaction zone, which is characterized in that use Al2O3、SiC The nano ceramic powder of bi-component proportion, wherein Al2O325-50wt%, the SiC for accounting for nanometer scale ceramics total powder quality account for nanometer The 25-50wt% of grade ceramic powders gross mass.
3. insulated high-strength amberplex according to claim 1 non-reaction zone, which is characterized in that the asphalt mixtures modified by epoxy resin Lipoprotein mixture is formed mixed using mass ratio 1:0.1-1:1 bisphenol A type epoxy resin and aliphatic glycidyl ether epoxy resin Close object.
4. insulated high-strength amberplex according to claim 1 non-reaction zone, which is characterized in that polynary amine-type cure Agent composition is made of diethylenetriamine, tetra-methylenedimine and di-2-ethylhexylphosphine oxide hexamethylene alkanamine, and wherein diethylenetriamine accounts for polynary The 20-50wt% of amine-type cure agent composition gross mass, tetra-methylenedimine account for polynary amine curing agent mixture gross mass 20-50wt%, di-2-ethylhexylphosphine oxide hexamethylene alkanamine account for the 5-15wt% of polynary amine curing agent mixture gross mass.
5. a kind of insualtion resin composition coated such as any insulated high-strength amberplex non-reaction zone claim 1-4 Preparation method, which comprises the following steps:
S1. epoxy resin is weighed in proportion, is uniformly mixed, and epoxy resin composition is obtained；
S2. nanometer scale ceramics powder is weighed in proportion to stir evenly when being added in epoxy resin composition；
S3. weighing active dispersing agents are added in step S2 obtained component in proportion, are added while stirring until stirring evenly；
S4. it weighs polynary amine curing agent, is added in step S3 component in proportion, be added while stirring until stir evenly, obtained Obtain insulating resin mixture.
6. a kind of preparation method of any insulated high-strength amberplex non-reaction zone as described in claim 1-4, special Sign is, insulating resin mixture is added in Full-automatic coating machine, is coated to amberplex non-reaction zone, coated strands Part are as follows: gas source is nitrogen, gas pressure 0.05-0.5MPa, spray head and amberplex surface distance 0.1-10cm, spray head scanning frequency 0.1-50cm/s, the amberplex after coating is dry under room temperature, obtains having the ion of insulated high-strength non-reaction zone to hand over Change film.
7. a kind of all-vanadium flow battery amberplex, which is characterized in that non-reaction zone coating is any as described in claim 1-4 Kind insualtion resin composition.
CN201810384926.3A 2018-04-26 2018-04-26 Ion exchange membrane with insulating high-strength non-reaction zone and preparation method thereof Active CN110416582B (en)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20010008734A1 (en) * 1998-11-12 2001-07-19 Dupasquier Aurelien Polymeric mesoporous separator elements for laminated lithium-ion rechargeable batteries
CN101533915A (en) * 2008-03-11 2009-09-16 上海清能燃料电池技术有限公司 Membrane electrode and current collecting board element of electrochemical cell and electrochemical cell module
CN102838921A (en) * 2012-09-28 2012-12-26 北京天山新材料技术股份有限公司 Brushed high-strength abrasion-resistant anticorrosive coating and preparation method
CN103074022A (en) * 2012-12-29 2013-05-01 东莞市松山湖微电子材料研发中心 Heat-conducting electronic pouring sealant containing modified filler
CN106558662A (en) * 2015-09-28 2017-04-05 大连融科储能技术发展有限公司 Ion-conductive membranes, using the flow battery and preparation method of the ion-conductive membranes

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20010008734A1 (en) * 1998-11-12 2001-07-19 Dupasquier Aurelien Polymeric mesoporous separator elements for laminated lithium-ion rechargeable batteries
CN101533915A (en) * 2008-03-11 2009-09-16 上海清能燃料电池技术有限公司 Membrane electrode and current collecting board element of electrochemical cell and electrochemical cell module
CN102838921A (en) * 2012-09-28 2012-12-26 北京天山新材料技术股份有限公司 Brushed high-strength abrasion-resistant anticorrosive coating and preparation method
CN103074022A (en) * 2012-12-29 2013-05-01 东莞市松山湖微电子材料研发中心 Heat-conducting electronic pouring sealant containing modified filler
CN106558662A (en) * 2015-09-28 2017-04-05 大连融科储能技术发展有限公司 Ion-conductive membranes, using the flow battery and preparation method of the ion-conductive membranes

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