CN110283345A - A kind of starch silver nanowires flexible composite electrode material and preparation method thereof - Google Patents
A kind of starch silver nanowires flexible composite electrode material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of starch silver nanowires flexible composite electrode materials and preparation method thereof；Method includes the following steps: the preparation of (1) crosslinked starch；(2) preparation of graft copolymerization starch；(3) preparation of flexible Modified Starch film；(4) preparation of combination electrode material.It is raw material by high Cross-linked, graft copolymerization, saponification preparation grafting shuttle base starch using potato starch, then prepares starch film, bar rubbing method prepares combination electrode in conjunction with silver nanowires.Product of the graft copolymerization starch of polar functionalities after being saponified has superabsorbency, the deionized water for the hundred times to thousands of times that it is self-possessed can be absorbed, and to certain ions such as Cu2+,Cr2+,Pb2+With suction-operated.The stronger electric conductivity of silver nanowires and antibiotic property can play the antiseptic property of electrochemistry and the antibacterial ability of silver nanowires simultaneously, and the two is compound to prepare degradable electrode material, and in electrochemical disinfection, ionic adsorption, the fields such as sensor, which have, to be widely applied.
Description
Technical field
The invention belongs to the preparation technical field of combination electrode material more particularly to a kind of starch silver nanowires flexible compounds
Electrode material and preparation method thereof.
Background technique
21 century, the mankind face huge challenge in terms of energy crisis and environmental protection, and people have turned one's attention to green
The exploitation of the color energy and the novel recyclable materials of invention.Forefathers are existing with cellulose, and starch, chitosan etc. is raw material, with conduction
Material graphene, silver nanowires, polyaniline etc. combine and prepare composite conducting material, are applied to solar battery, and electrode is flexible saturating
Bright conductive film and sensor etc..
Summary of the invention
It is flexible to provide a kind of starch silver nanowires for the shortcomings that it is an object of the invention to overcome the above-mentioned prior art and deficiency
Combination electrode material and preparation method thereof.The present invention, which is made from starch, to be modified, and high Cross-linked, graft copolymerization, soap are passed through
Change hydrolysis preparation grafting shuttle base starch, starch film is made in the starch of modified, is then made in conjunction with conductive material silver nanowires
Standby combination electrode material, in conjunction with the strong absorptive of grafting shuttle base starch, strong absorption property and silver nanowires to metal ion
Antibiotic conductive effect, can be applied to electrochemistry, sensor, the fields such as water process.
The present invention is achieved through the following technical solutions:
A kind of starch silver nanowires flexible composite electrode material preparation method, includes the following steps:
Step 1: crosslinked starch preparation
Starch milk solution is configured, preheating adjusts pH, and the mixed solution of acetic anhydride and citric acid, water-bath, mistake is added
Filter is washed, dry；
Step 2: graft copolymerization starch preparation
Crosslinked starch lotion is configured, nitrogen flooding is passed through by oxygen, ammonium ceric nitrate and acrylonitrile is added by reaction after saponification
Hydrolysis adjusts pH value；
Step 3: Modified Starch film preparation
Starch milk solution in step 2 is taken, glycerol stirring centrifugation is added, pours into culture dish the tape casting film forming, drying for standby；
Step 4: combination electrode material preparation
Silver nanowires is dissolved in aqueous isopropanol, deionized water impregnates starch film demoulding, will be silver-colored using coating bar
Nano wire even application is on starch film, drying at room temperature, cuts.
In above-mentioned steps one: the acetic anhydride and citric acid mixed solution additional amount and starch quality relationship be 0.04~
0.06mL/g, citric acid and acetic anhydride ratio are 1:30~1:40.
In above-mentioned steps two: ammonium ceric nitrate is 1%~3% with starch quality relationship.
In above-mentioned steps two: the saponification refers to that, with 5%~10% sodium hydroxide, 75 DEG C~80 DEG C reactions are extremely
Color from bronzing be changed into it is faint yellow until.
In above-mentioned steps two: it is 0.5~1mL/g that acrylonitrile and starch quality relationship, which is added, the condition of the reaction be
It is stirred 45~60 minutes under 40 DEG C~60 DEG C environment；The concentration of the starch milk solution is 4%~6%.
In above-mentioned steps three: amounts of glycerol is added and starch solution magnitude relation is 10%~20%.
In above-mentioned steps one: the concentration of the starch milk solution is 30%~40%；The time of the preheating be 5~
10min, the temperature of preheating are 50~60 DEG C, and pH value is adjusted to 9-12 (final ph adjusts preferably 6.5~8)；
The temperature of the water-bath is 50~60 DEG C, and the time of water-bath is 100~120min；
The washing is alternately washed with acetone and water, and drying is with the 40 DEG C of dryings of (10HS type) Constant Temp. Oven.
Above-mentioned steps three: it is 20~30ml that the starch film preparation, which takes starch milk amount of solution,；The time of the centrifugation is 5-
8min, 3000~5000r/min of revolving speed；Dry is (10HS type) Constant Temp. Oven, 30 DEG C~50 DEG C dry 12~14h.
Above-mentioned steps four: entering isopropanol dissolution for silver nanowires when the coating, adjusts concentration to 10mg/mL；The room
Temperature is dry for 12~16h of natural drying；The line width of the coating bar is 50 μm；The number of plies of the coating is 1~5 layer；It is described
Cutting area is 1~3cm2It is rectangular.
The above-mentioned preparation method of the present invention, can get starch silver nanowires flexible composite electrode material.
The present invention is based on the principle that being made from starch through high Cross-linked, graft copolymerization, saponification preparation connects
Branch shuttle base starch, then starch film is made in conjunction with silver nanowires in starch.It is copolymerized by cross-linked graft, is drawn on starch molecular chain
Richer active group is entered, a kind of efficient water absorbing agent and adsorbent has been made, in addition, crosslinked starch molecule is by ball
Shape molecule in close is accumulated, and the structure feature of crystalline high polymer is showed, and Carboxyl-containing Starch is typical amorphous state
Structure, grafting molecules chain combination on the high crosslinked starch of 3 D stereo shape, form it is loose, in coralloid random
Microcellular structure, this microcellular structure increase specific surface area, so that it is not only present in carboxyl grafting to the adsorption site of ion and form sediment
Powder molecular surface, additionally it is possible to diffuse to any possible site-COONa, significantly increase adsorption capacity.
After silver nanowires is powered, special linear nanometer mechanism greatly reduces charge transtion, electric current low damage on line
Consume flow at high speed, surface accumulates a large amount of charges, generated around silver nanowires it is high-intensitive, can penetrating cell film, cause electricity to be worn
Hole leads to bacterial death.Grafting shuttle base starch not only has adsorptivity to water, also has strong absorption property, net to certain ions
Shape structure can close bind metal ion, then be prepared into starch film, synthesized in conjunction with conductive material silver nanowires multiple
Composite electrode material, it is common to play the two advantage.
Compared with prior art, the invention has the advantages that and advantage:
Combination electrode material is graft copolymerization starch film in conjunction with conductive silver nano wire, except have starch and synthesis high score
It is a kind of novel electrode material also with the characteristic of silver nanowires, tool has been widely used except many properties of son.
Water imbibition of the invention.Starch molecule introduces a large amount of polar groups easily and water molecules after modifying, can be in water
Middle water absorption and swelling and do not dissolve, and infiltration rate is quickly, becomes a kind of colorless and transparent spawn after water suction, and work as surrounding
Moisture content be lower than gel when, it again can water releasing slowly, can Reusability, be often applied to super absorbent resin
Rouge.
Adsorptivity of the invention.Graft copolymerization starch has ion exchange, to certain ions such as Cu2+, Pb2+Deng
Metal cation has strong suction-operated, it is applied to resins exchange, adsorption capacity is high, and detachability is good, and reproducibility
It by force, is a kind of widely used novel renewable heavy metal ion adsorbed scavenger.
Silver nanowires of the present invention is conductive, and energization latter aspect energization silver nanowires surface generates high electric field breakdown simultaneously
Inactivation of bacterial, another aspect electrolytic process generate chlorine and are dissolved in the water, and the strong oxidizing property of free chlorine generates bactericidal effect.
Biodegradability of the invention.Starch degradable, it is renewable, it is easily decomposes in the natural environment, mitigate significantly
Problem of environmental pollution.
In step 1 of the present invention: the citric acid and acetic anhydride ratio are 1:30~1:40, and acetic anhydride dosage is more, product
The degree of cross linking it is higher, when mixed acid ratio be 1:30~1:40 when, the degree of cross linking is maximum value, continue growing mixed acid ratio, hand over
Connection degree starts to reduce.When acetic anhydride additional amount is reduced, mixed acid anhydride generates incomplete.Therefore choose mixed acid ratio (citric acid: second
Acid anhydrides) it is 1:30~1:40.The acetic anhydride and citric acid mixed solution additional amount and starch quality relationship be 0.04~
0.06mL/g, mixed acid additional amount is more, and the degree of cross linking is bigger.When mixed acid additional amount reaches 0.04~0.06mL/g, hand over
Joining angle value is maximum.But when continuing growing after the additional amount of mixed acid is more than 0.06mL/g, the degree of cross linking starts to reduce.Therefore it selects
It takes best mixed acid additional amount and dry weight of starch relationship between quality is 0.04~0.06mL/g.
In step 1 of the present invention: the time of the preheating is 5~10min, and the temperature of preheating is 50~60 DEG C, preheating temperature
Lower than 50 DEG C or the time is less than 5min, and activation energy needed for reacting is unable to reach, and reaction is incomplete；Preheating temperature be higher than 60 DEG C or when
Between more than 10min, initiator is easily assembled, and hinders monomer reflecting point on starch chain to spread, and declines grafting rate.
In step 2 of the present invention: ammonium ceric nitrate is 1%~3% with starch quality relationship, this is because with initiator nitre
Sour cerium ammonium concentration increases, grafting rate first increases and then decreases.Ammonium ceric nitrate concentration increases, and the free radical quantity on starch chain increases,
Graft reaction is caused to be accelerated, homopolymerization slows down, and grafting rate increases；When initiator ammonium ceric nitrate and starch quality relationship are greater than
When 3%, excess initiator aggregation hinders monomer reflecting point on starch chain to spread, and declines grafting rate.
In step 2 of the present invention: the condition of reaction is at 40 DEG C~60 DEG C, this is because at low temperature, polymerization reaction is not sent out
It is raw；With the raising of reaction temperature, grafting takes the lead in rising, rear to decline.Temperature, which rises, increases diffusion of the monomer to starch molecular chain,
Promote the swelling of starch；Increase the mobility of monomer and the collision probability with starch polymer, when temperature is greater than 60 DEG C, homopolymerization
Rate is accelerated, and transfer of the chain to monomer, grafting rate decline are hindered.
In step 2 of the present invention: the addition acrylonitrile is 0.5~1mL/g with starch quality relationship, this is because with
The increase of monomers acrylonitrile concentration, grafting efficiency take the lead in declining after rising with grafting.The reason of grafting rate rises, it may be possible to monomer
The probability for appearing in starch grains increases, thus collision probability increases between reactant.However, as monomer concentration is higher than 1mL/
G, homopolymerization is better than graft reaction, and declines grafting efficiency.The alkyl group length of monomer increases, and generates steric hindrance effect
It answers, declines grafting rate.
In step 3 of the present invention: the addition amounts of glycerol is 10%~20% with starch solution magnitude relation, this is because plus
It is insufficient to enter very few starch film flexibility, easily rupturable, the effect that additional amount excessively will affect graft plays.
In step 3 of the present invention: it is 20~30ml that the starch film preparation, which takes starch milk amount of solution, this is because taken amount mistake
It is too thin to will lead to film thickness less, bad mechanical property has an impact subsequent processing, and taken amount will lead to the too big shadow of thickness of electrode too much
Ring electrode flexibility.The time of the centrifugation is 5-8min, 3000~5000r/min of revolving speed, this is because centrifugal rotational speed is too low
Or the time it is too short be all easy to cause bubble except not leading to film out-of-flatness completely, the time is too long or revolving speed is too high will lead to starch solution
Deposition is uneven, and film forming is uneven, is unfavorable for the combination of film and conductive material.
In step 3 of the present invention: the drying is 12~16h of natural drying at room temperature, this is because oven drying speed mistake
Fastly, film is easily-deformable, and fold easily occurs in surface, is unfavorable for subsequent processing.
Detailed description of the invention
Fig. 1 is combination electrode material surface A FM figure prepared by embodiment 1.
Fig. 2 is combination electrode material surface A FM figure prepared by embodiment 2.
Fig. 3 is combination electrode material surface A FM figure prepared by embodiment 3.
Fig. 4 is combination electrode material electric conductivity (square resistance) variation diagram prepared by embodiment 1 to 3.
Fig. 5 is that combination electrode material electric conductivity (square resistance) prepared by embodiment 1 to 3 changes over time (stability)
Figure.
Fig. 6 is electrode Water absorption and absorbent time relational graph.
Fig. 7 is electrode to adsorption of metal ions performance and electrode quality relational graph.
Specific embodiment
The present invention is more specifically described in detail combined with specific embodiments below.
Embodiment 1
Step 1: weighing 6g potato starch in conical flask with electronic balance, 20mL distilled water is added and is configured to
30% starch emulsion, stirs evenly, 50 DEG C of preheating 10min in the bath that discharges water, after being measured pH with test paper and be adjusted to 9, slowly
0.36mL is added, ratio is the mixed solution of 0.01mL citric acid and 0.35mL acetic anhydride, 55 DEG C of water-baths, during reaction
It keeps pH constant, reacts 100min.After reaction, pH value of solution is adjusted to 7, then is filtered, and is washed, be dry, pulverize, most
After obtain finished product.
Step 2: taking gained crosslinked starch in 3g that 50mL deionized water is added, stirs evenly, is passed through nitrogen in conical flask
Or so gas half an hour drives away wherein oxygen, adds 0.03g ammonium ceric nitrate, stirs evenly, is subsequently added into 3mL acrylonitrile at 40 DEG C
Left and right stirring 55 minutes carries out saponification with 5% sodium hydroxide, while system temperature is controlled 85 DEG C, reaction to system
Color from bronzing be changed into it is faint yellow until, then cool down, with 2% salt acid for adjusting pH to subacidity.
Step 3: taking above-mentioned starch solution 30ml, 3mL glycerol is added and stirs evenly, 5000r/min is centrifuged 5min, is placed in
In culture dish, the tape casting film forming, 30 DEG C of dry 13h in baking oven, distilled water immersion taking-up starch film.
Step 4: silver nanowires is dispersed in isopropanol, then the silver nanowires solution for being made into 10mg/mL uses
Coating bar (line width is 50 μm) is coated uniformly on starch film,, will after solvent volatilizees naturally at room temperature with a thickness of 1 layer
Combination electrode material natural drying at room temperature 16h, it is final to obtain the uniform electrode material in surface, it is cut into the rectangle of 1X3cm, electrode
Area be 3cm2。
Embodiment 2
Step 1: weighing 6g potato starch in conical flask with electronic balance, 15mL distilled water is added and is configured to
40% starch emulsion, stirs evenly, 55 DEG C of preheating 7min in the bath that discharges water, after being measured pH with test paper and be adjusted to 12, slowly
The 0.31mL of starch quality is added, ratio is 0.01mL citric acid, and the mixed solution of 0.3mL acetic anhydride, 60 DEG C of water-baths are reacting
During to keep pH constant, react 110min.After reaction, pH value of solution is adjusted to 8, then is filtered, and is washed, is done
It is dry, it crushes, finally obtains finished product.
Step 2: taking gained crosslinked starch in 2g that 50mL deionized water is added, stirs evenly, is passed through nitrogen in conical flask
Or so gas half an hour drives away wherein oxygen, adds 0.04g ammonium ceric nitrate, stirs evenly, is subsequently added into 1.5mL acrylonitrile 60
DEG C or so stirring 45 minutes, carries out saponification with 10% sodium hydroxide, while system temperature is controlled 75 DEG C, reacts to body
Be color from bronzing be changed into it is faint yellow until, then cool down, with 2% salt acid for adjusting pH to subacidity.
Step 3: taking above-mentioned starch solution 25ml, 4ml glycerol is added and stirs evenly, 4000r/min is centrifuged 6min, is placed in
In culture dish, the tape casting film forming, 50 DEG C of dry 12h in baking oven, distilled water immersion taking-up starch film.
Step 4: silver nanowires is dispersed in isopropanol, it is made into the silver nanowires solution of 10mg/mL, is then adopted
It is coated uniformly on starch film with coating bar (line width is 50 μm), with a thickness of 3 layers, after solvent volatilizees naturally at room temperature,
It is final to obtain the uniform electrode material in surface by combination electrode material natural drying at room temperature 12h, it is cut into the rectangle of 1X1cm, electricity
The area of pole is 1cm2。
Embodiment 3
Step 1: weighing 7g potato starch in conical flask with electronic balance, 20mL distilled water is added and is configured to
35% starch emulsion, stirs evenly, 60 DEG C of preheating 5min in the bath that discharges water, after being measured pH with test paper and be adjusted to 10, slowly
The 0.28mL of addition starch quality, mixed solution of the ratio for 0.007mL citric acid and 0.273mL acetic anhydride, 50 DEG C of water-baths,
It to keep pH constant during reaction, react 120min.After reaction, pH value of solution is adjusted to 6.5, then is filtered, and is washed
It washs, dry, pulverize, finally obtain finished product.
Step 2: taking gained crosslinked starch in 2.5g that 50mL deionized water is added, stirs evenly, is passed through in conical flask
Or so nitrogen half an hour drives away wherein oxygen, adds the aqueous solution of 0.075g ammonium ceric nitrate, stirs evenly, is subsequently added into
1.25mL acrylonitrile stirs 60 minutes at 50 DEG C or so, carries out saponification with 7% sodium hydroxide, while by system temperature control
80 DEG C of system, reaction to system color from bronzing be changed into it is faint yellow until, then cool down, with 2% salt acid for adjusting pH to micro-
It is acid.
Step 3: taking above-mentioned starch solution 20ml, 2ml glycerol is added and stirs evenly, 3000r/min is centrifuged 8min, is placed in
In culture dish, the tape casting film forming, 40 DEG C of dry 14h in baking oven, distilled water immersion taking-up starch film.
Step 4: silver nanowires is dispersed in isopropanol, it is made into the silver nanowires solution of 10mg/mL, is then adopted
It is coated uniformly on starch film with coating bar (line width is 50 μm), with a thickness of 5 layers, after solvent volatilizees naturally at room temperature,
It is final to obtain the uniform electrode material in surface by combination electrode material natural drying at room temperature 14h, it is cut into the rectangle of 1X2cm, electricity
The area of pole is 2cm2。
As described above, the present invention can be better realized.
The present invention passes through high Cross-linked, graft copolymerization, saponification preparation grafting shuttle Ji Dian by raw material of potato starch
Powder, then starch film is prepared, bar rubbing method prepares combination electrode in conjunction with silver nanowires.The graft copolymerization starch of polar functionalities
Product after being saponified has superabsorbency, the deionized water for the hundred times to thousands of times that it is self-possessed can be absorbed, and to certain
A little ions such as Cu2+,Cr2+,Pb2+With suction-operated.The stronger electric conductivity of silver nanowires and antibiotic property, can play electricity simultaneously
The antiseptic property of chemistry and the antibacterial ability of silver nanowires, the two is compound to prepare degradable electrode material, in electrochemical disinfection, from
Son absorption, the fields such as sensor, which have, to be widely applied.
Embodiment of the present invention are not limited by the above embodiments, other are any without departing from Spirit Essence of the invention
With changes, modifications, substitutions, combinations, simplifications made under principle, equivalent substitute mode should be, be included in of the invention
Within protection scope.
Claims (10)
1. a kind of starch silver nanowires flexible composite electrode material preparation method, it is characterised in that include the following steps:
Step 1: crosslinked starch preparation
Starch milk solution is configured, preheating adjusts pH, and the mixed solution of acetic anhydride and citric acid, water-bath is added, and filtering is washed
It washs, it is dry；
Step 2: graft copolymerization starch preparation
Crosslinked starch lotion is configured, nitrogen flooding is passed through by oxygen, ammonium ceric nitrate and acrylonitrile is added and is hydrolyzed by reaction after saponification,
Adjust pH value；
Step 3: Modified Starch film preparation
Starch milk solution in step 2 is taken, glycerol stirring centrifugation is added, pours into culture dish the tape casting film forming, drying for standby；
Step 4: combination electrode material preparation
Silver nanowires is dissolved in aqueous isopropanol, deionized water impregnates starch film demoulding, using coating bar by silver nanoparticle
Line even application is on starch film, drying at room temperature, cuts.
2. starch silver nanowires flexible composite electrode material preparation method according to claim 1, it is characterised in that step 1
In: the acetic anhydride is 0.04~0.06mL/g, citric acid and second with citric acid mixed solution additional amount and starch quality relationship
Anhydride ratio is 1:30~1:40.
3. starch silver nanowires flexible composite electrode material preparation method according to claim 1, it is characterised in that step 2
In: ammonium ceric nitrate is 1%~3% with starch quality relationship.
4. starch silver nanowires flexible composite electrode material preparation method according to claim 3, it is characterised in that step 2
In: the saponification refers to that, with 5%~10% sodium hydroxide, 75 DEG C~80 DEG C reactions are changed into color from bronzing
Until faint yellow.
5. starch silver nanowires flexible composite electrode material preparation method according to claim 4, it is characterised in that step 2
In: it is 0.5~1mL/g that acrylonitrile and starch quality relationship, which is added, and the condition of the reaction is stirred under 40 DEG C~60 DEG C environment
It mixes 45~60 minutes；The concentration of the starch milk solution is 4%~6%.
6. starch silver nanowires flexible composite electrode material preparation method according to claim 1, it is characterised in that step 3
In: amounts of glycerol is added and starch solution magnitude relation is 10%~20%.
7. starch silver nanowires flexible composite electrode material preparation method according to claim 2, it is characterised in that step 1
In: the concentration of the starch milk solution is 30%~40%；The time of the preheating is 5~10min, the temperature of preheating is 50~
60 DEG C, pH value is adjusted to 9~12；
The temperature of the water-bath is 50~60 DEG C, and the time of water-bath is 100~120min；
The washing is alternately washed with acetone and water, and drying is with 40 DEG C of dryings in Constant Temp. Oven.
8. starch silver nanowires flexible composite electrode material preparation method according to claim 1, it is characterised in that step 3:
It is 20~30ml that the starch film preparation, which takes starch milk amount of solution,；The time of the centrifugation be 5-8min, revolving speed 3000~
5000r/min；Dry is Constant Temp. Oven, 30 DEG C~50 DEG C dry 12~14h.
9. starch silver nanowires flexible composite electrode material preparation method according to claim 1, it is characterised in that step 4:
Silver nanowires is entered into isopropanol dissolution when the coating, adjusts concentration to 10mg/mL；The drying at room temperature be spontaneously dry 12~
16h；The line width of the coating bar is 50 μm；The number of plies of the coating is 1~5 layer；The cutting area is 1~3cm2Side
Shape.
10. the starch silver nanowires flexible composite electrode material that preparation method described in any one of claim 1-9 obtains.
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