CN109776851A - A kind of bacteria cellulose/metal sulfide plural gel and preparation method thereof and conductive processing method - Google Patents
A kind of bacteria cellulose/metal sulfide plural gel and preparation method thereof and conductive processing method Download PDFInfo
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Abstract
The present invention relates to composite materials and field of energy source materials, more particularly to a kind of bacteria cellulose/metal sulfide plural gel and preparation method thereof and conductive processing method, the purpose is to be its application effect in electrochemical field of raising, and provide a kind of conductive processing method that chemical property enhancing is carried out to it.The technical program preparation method step includes: to dissolve one or more salt and be formulated as maceration extract；Pretreated bacteria cellulose aquagel is placed in above-mentioned maceration extract and carries out impregnation；The bacteria cellulose aquagel of adsorptive liquid is put into the solution of sulfur-bearing and carries out hydro-thermal process, obtains plural gel；It is subsequent to be replaced by multiple solvent, it is then dried and obtains a variety of BC/ metal sulfide composite aerogels.It is fluff structure after plural gel processing, there is high specific surface area and good electric conductivity.
Description
Technical field
The present invention relates to field of energy source materials more particularly to a kind of bacteria cellulose/metal sulfide plural gel and its
Preparation method and conductive processing method.
Background technique
Bacteria cellulose (BC) is a kind of noticeable, environment amenable nano-fiber materials, mainly by
Bacterium is produced by D-Glucose.It is 50~80nm, with a thickness of 3~8nm nanofiber that it, which is by a series of continuous width,
The ribbon of the three-dimensional porous miniature reticular structure of composition.Bacteria cellulose has high-purity, high-crystallinity, high-hydroscopicity, excellent
The performances such as elegant stability and good bioaffinity, contain hydroxyl abundant, can be by stronger interaction by nothing
The different nano materials absorption of machine and conductive polymer nanometer particle or nano wire etc..Conducting polymer (CPs) has lightweight, soft
Property, good electric conductivity and height ratio capacity, transition metal metal sulfide has height ratio capacity and good redox reversible
Performance.
A large amount of holes are formed between the fiber and fiber of BC gel, constitute three-dimensional space net structure.BC fiber surface
With a large amount of hydroxy functional group, this unique structure and properties convenient for fiber easily adsorbing metal ions and make metal from
Son is spread in BC hydrogel, provides high activity region and big surface area for the growth of particle.Fluffy spongy shape it is thin
Fungin/metallic compound plural gel shows excellent flexibility, and the composite material is at low cost, adhesive-free.BC
Fiber not only plays a crucial role in terms of the growth for metal compound particles provides nucleation site, but also limits
The size of particle increases, and can also be effectively prevented the Severe aggregation of pure particle, to obtain higher specific surface area.
But at present for BC/ metallic compound plural gel preparation research ground zero, drying means is more single, such as heats
Dry method is very easy to so that the structure of BC gel changes or fall damage, and drying process is difficult to BC gel
Microstructure forms protection, and controllability is poor, and it is tight to also result in BC gel structure using the dry method of directly freezed
It destroys again, cannot keep its original pattern and forms " sheet " gel of consolidation.
Just such as a kind of Patent Office of the People's Republic of China's battery based on N doping carbonization bacteria cellulose disclosed on April 26th, 2017
The application for a patent for invention of pole, lithium-sulfur cell and preparation method thereof, application notification number are CN106601990A, and it discloses a kind of bases
In the N doping carbonization anode of bacteria cellulose, lithium-sulfur cell and preparation method thereof.The present invention is raw using bacteria cellulose
The source N needed in object incubation carries out N doping, prepares cell positive material；By by ultralight carbonization bacteria cellulose interlayer
Compound preparation with porous carbon has the battery sandwich of strong adsorption capacity；It is fine by ion selectivity barrier layer Nafion and bacterium
The combination for tieing up plain aeroge prepares battery diaphragm material, and the anode based on N doping carbonization bacteria cellulose, carbonization is thin
Fungin function interlayer, Nafion/BC diaphragm are assembled into lithium-sulfur cell.The invention is adulterated by N element, function interlayer draws
Enter, Nafion/BC diaphragm is used in combination, stage construction controls polysulfide and spreads to cathode of lithium, realizes and expands for polysulfide
It is scattered it is multistage inhibit, effectively control shuttle effect, the Li-S battery for assembling formation has a height ratio capacity, high coulomb efficiency and steady
Fixed cycle performance.But carried out by the way of heated drying in preparation method, preparation-obtained electrode material loses
The performance characteristics that bacteria cellulose itself has, lose high-specific surface area and high flexibility.
A kind of for another example Patent Office of the People's Republic of China's sandwich proton exchange of bacteria cellulose-Nafion disclosed on August 12nd, 2015
Film and the invention patent mandate of preparation and application, Authorization Notice No. CN102694139B are related to a kind of bacteria cellulose-
The sandwich proton exchange membrane of Nafion, the sandwich proton exchange membrane are BC-Nafion-BC or Nafion-BC-Nafion structure；It should
The sandwich proton exchange hybrid films of invention have lower methanol permeability, higher proton conductivity and thermal stability, in first
It has a good application prospect in alcohol fuel battery as diaphragm, and preparation is simple, environmental pollution is small.But it is dry
" sheet " gel that dry mode equally exists and destroy the microstructure of bacterial cellulose gel, forms it into consolidation leads to not
The problems such as design feature or drying efficiency of effective use bacterial cellulose gel itself are low, drying is not thorough.
Patent Office of the People's Republic of China disclosed the carbon pipe and carbon Nanowire of a kind of sulfide growth based on cobalt on February 22nd, 2017
The preparation method application for a patent for invention of composite aerogel is tieed up, application No. is CN106422997A.The invention is related to the sulphur based on cobalt
The carbon nanotube of compound growth and the preparation method of carbon nano-fiber composite aerogel.The preparation method includes: first by bacterium fibre
Dimension hydrogel be immersed in containing metal salt, urea, thiocarbamide mixed solution in, it is fine that the bacterium is then obtained by Pintsch process
Carbon pipe and carbon nano-fiber composite aerogel based on metal sulfide growth derived from dimension element.This kind of preparation method has preparation
Process is simple, environmental-friendly, low power consuming and can be with large scale preparation the advantages that.In addition, the three-dimensional material tool of this method preparation
There are porous network structure and good electric conductivity, the carbon pipe based on metal sulfide grain growth is wrapped on carbon nano-fiber,
More complicated three-dimensional net structure is formd, specific surface area greatly increases.In photoelectrocatalysis, electrochemistry and heavy metal ion
It has broad prospects in the application such as absorption.But the art solutions are mainly used for preparing carbon pipe compound with carbon nano-fiber
Aeroge, and it is easy to damage bacterial cellulose three-dimensional porous network structure in liquid-nitrogen freeze drying first, it is obtained
Composite aerogel be consolidation " sheet "；And the arid cycle of supercritical drying is long, under low output, it is with high costs, it is difficult
To realize volume production,.In subsequent high temperature cracking process, original structure is destroyed again, and final obtained aeroge is
It is powdered, the original advantage of bacteria cellulose is lost, it is lower to the excellent in performance utilization rate of bacteria cellulose.
In addition, the preparation of Peng Shuo bacteria cellulose-base flexible composite electrode material and the weaving of the performance study Wuhan [D] are big
It learns, is studied in terms of having carried out capacitor to bacteria cellulose (BC)/metallic compound compound preparation electrode in 2017. 1 texts.
And has very much and be pointedly prepared for PPy/NiS/BC nanofiber combination electrode material, be using BC film as substrate, first
BC film is immersed in NiSO4In solution, it is then immersed in the Na of corresponding solubility2The bacteria cellulose containing NiS is obtained in S solution
Composite membrane；It places it in stirring in pyrroles's aqueous solution and passes through FeCl3As oxidant, 2h is reacted under the conditions of ice-water bath, is utilized
In-situ oxidizing-polymerizing method obtains.PPy/CuS/BC and PPy/CoS/BC nanofiber combination electrode is prepared for similar method
Material.
Chen W,Yu H,Lee S Y,et al.Nanocellulose:a promising nanomaterial for
Advanced electrochemical energy storage. [J] .Chemical Society Reviews, 2018. 1
Equally be referred in text bacteria cellulose (BC) in terms of electrochemical energy storage using great prospect.
Summary of the invention
To solve the research for BC plural gel at present and few, the BC/ especially in the metal material field of electrochemistry
The research of metallic compound plural gel is limited, and can not be to bacteria cellulose/excellent electrification of metal sulfide plural gel
The problem of performance is utilized is learned, the present invention provides a kind of bacteria cellulose/metal sulfide plural gel and its preparation sides
Method and conductive processing method.Its primary and foremost purpose is to provide that a kind of environmental-friendly and efficient to prepare bacteria cellulose/metal sulfide compound
The method of gel, and a kind of carry out to it effectively is provided on this basis to improve its application effect in electrochemical field
The conductive processing method of chemical property enhancing.
To achieve the above object, the invention adopts the following technical scheme:
A kind of preparation method of bacteria cellulose/metal sulfide plural gel, the preparation method includes following preparation step:
1) it prepares maceration extract: the dissolution of one or more salt is formulated as maceration extract；
2) load dipping: pretreated bacterial cellulose gel is impregnated in maceration extract obtained by step 1) and is carried out at dipping
Reason；
3) hydro-thermal process: the bacterial cellulose gel through step 2) impregnation is put into the solution of sulfur-bearing and is carried out at hydro-thermal
Reason, obtains plural gel；
4) displacement drying: carrying out multiple solvent displacement to the plural gel through step 3) hydro-thermal process, be then dried, dry
After obtain bacteria cellulose/multi-element metal sulfide plural gel,
Wherein, containing at least one metal target element in the step 1) maceration extract, the metal target element include iron,
Vanadium, nickel, copper, cobalt and rhenium.
The method of the present invention is easy to operate, and can prepare single metallic compound or various metals according to use demand
It closes object cooperation BC gel and prepares plural gel, raw material sources are extensive, and preparation cost is low, performance controllability is strong, and maceration extract
And solution used in water-heat process can be repeatedly utilized so that, very environmentally friendly, obtained plural gel is able to maintain BC gel
The puffy of itself keeps many-sided excellent in performance such as its high porosity, high-specific surface area and softness.Ferro element can be nitric acid
The soluble ferric iron salts such as iron, ferric sulfate, iron chloride, same nickel element, copper and cobalt element etc. can be from a wealth of sources and price
Cheap soluble-salt, rhenium element source can be used for preparing type very for soluble-salts, i.e. the method for the present invention such as rehenic acid ammoniums
More bacteria cellulose/metal sulfide plural gel, and optional raw material sources are very extensive, and the original of low cost can be selected
Material.
Preferably, the preprocessing process of the step 2) bacterial cellulose gel is to be impregnated carefully using sodium hydroxide solution
Fungin gel is simultaneously washed to neutrality, the when a length of 8~16h for being placed in impregnation in maceration extract.
Preprocessing process the specific steps are the sodium hydroxide solution standings using 0.8~1.25wt%, and 70~85
It is carried out under the conditions of DEG C, continues 100~150min, pre-processed and can remove bacterial cellulose gel surface and intrapore grease etc.
Impurity improves the effect of impregnation, enhances the ability of metal ion in absorbing load maceration extract, the sodium hydroxide of low concentration can
It is avoided to damage bacterial cellulose gel, washing to eluate pH value is 6.5~7.5 after dipping is completed.
And impregnation time too short its metal component for absorbing absorption that will lead to is low, overlong time is then easy to bacterium fibre
The gap for tieing up plain gel results in blockage and reduces its performance instead.
Preferably, a length of 3 when the step 3) hydro-thermal process~for 24 hours, solution used in hydro-thermal process is obtained by step 1)
The combination solution or organic solution of maceration extract obtained by maceration extract, step 1).
The solution system of hydro-thermal process is adjusted according to the composition metal ingredient of load, can directly adopt prepared leaching
Maceration extract extraction raffinate after stain liquid or impregnation, is also compounded and carries out hydro-thermal again, can also directly adopt thiourea solution or remaining
Sulfur-containing organic solution is as hydrothermal solution system.
Preferably, the step 4) solvent is replaced into the displacement of three-step approach solvent, detailed process are as follows: sequentially successively utilize
Water, ethyl alcohol and the tert-butyl alcohol impregnate plural gel.
Displacement water is carried out using remaining solution after hydro-thermal process in water displacement BC gel, then with ethyl alcohol, finally with tertiary fourth
The structural stability that BC gel in drying process can be improved is dried after carrying out complete solvent displacement in alcohol displacement ethyl alcohol again,
Especially in freeze-drying, it not will form skeleton structure deformation, makes the three-dimensional porous network structure both shrinks of script, integrally becomes
Flat " scraps of paper shape " and cause performance sharp fall, on the other hand carrying out solvent displacement can be avoided the residual of water-heat process
Crystallization is precipitated in solution in subsequent drying process, adversely affects to whole BC/ metal sulfide plural gel performance.
Preferably, step 4) is described dry using freeze-drying.
Freeze-drying compared to heated drying processing, with higher drying effect, and after solvent is replaced not
The advantages of damage being generated to structure, keep the original high flexibility of BC gel, high-specific surface area and high porosity.
A kind of bacteria cellulose/metal sulfide plural gel, the bacteria cellulose/metal sulfide plural gel are
Gel with high porosity and high-specific surface area, matrix are solidifying for the bacteria cellulose containing three-dimensional porous network structure
Glue, three-dimensional porous structure inside doping contain metal sulfide grain.
Continuous nanofiber of the BC gel by diameter less than 100nm forms, and a large amount of holes are formed between fiber and fiber,
Constitute three-dimensional space net structure.BC fiber surface has a large amount of hydroxy functional group, and this unique structure and properties are just
It easily adsorbing metal ions and spreads metal ion in BC hydrogel in fiber, provides high activity for the growth of particle
Region and big surface area.Bacteria cellulose/metal sulfide plural gel shows excellent flexibility, and the composite material
At low cost, adhesive-free.BC fiber not only plays in terms of the growth for metal compound particles provides nucleation site to Guan Chong
The effect wanted, and the size for also limiting particle increases, to obtain higher specific surface area.And bacterium of the invention is fine
Tieing up element/metal sulfide plural gel is obtained by freeze drying process after improved multiple solution replacement, is remained still
Gel with high porosity, high-specific surface area and high flexibility, not " scraps of paper shape " compound, preferably remains original BC
The excellent in performance feature of gel.
Preferably, the metal sulfide grain is spheric granules.
Spheric granules is compared to remaining special-shaped particle, and the uniformity of large specific surface area, diffusion is higher, therefore plural gel
Performance it is also more excellent.
A kind of conductive processing method of bacteria cellulose/metal sulfide plural gel, the conductive processing method are carbon
Change processing or the processing of polypyrrole cladding or polyaniline-coated processing.
The electric conductivity of BC/ metal sulfide plural gel is improved using conductive processing method, it is possible to increase it is in electrochemistry
Application range in field, such as can be as high-performance flexible electrode.
Preferably, the step of carbonization treatment are as follows: will be by pretreated bacterial cellulose gel in protection gas
It is heated to 230~280 DEG C in atmosphere and keeps the temperature 1.5~3h, then raise temperature to 550~620 DEG C and keeps the temperature 1.5~3h furnace cooling；
The step of polypyrrole cladding processing are as follows: the plural gel obtained after hydro-thermal is placed in pyrroles's aqueous solution and is stirred, it is then slow
It is slow that equivalent ferric chloride solution is added dropwise, 1.5~3h is reacted after being added dropwise to complete under the conditions of -5~2 DEG C；The polyaniline-coated processing
The step of are as follows: the plural gel obtained after pretreated bacterial cellulose gel or hydro-thermal is placed in aniline monomer solution
Stirring is then added oxidant and carries out 2~4h of in-situ polymerization.
Polypyrrole (PPy) layer is uniformly coated on BC fiber surface, so as to cause nanofiber diameter increase, due to pyrroles
Effect between the imine group of the inside and the hydroxyl of cellulose forms hydrogen bond inside PPy/BC composite membrane, and hydrogen bond plays one
Kind helps PPy layers along nanofiber growth and prevents the effect of extensive agglomeration, and PPy and metal is added
Compound does not change the intrinsic flexibility of BC；Polyaniline-coated processing makes monomer aniline in BC gel-in-matrix by oxidation polymerization
Or the plural gel surface after hydro-thermal carries out in-situ polymerization, increases substantially its electric conductivity, and it is solidifying not change former BC
The intrinsic excellent performance such as the flexibility of glue material；Contain the functional group with higher intensity similar with original BC after BC carbonization,
Show that most of functional groups still have after heat treatment, 800 DEG C of heat treatment temperature is not used more than here, because more
The self-support structure of bc-CNFs is destroyed at a temperature of high.
The beneficial effects of the present invention are:
1) present invention has filled up the technology vacancy of BC/ metal sulfide plural gel, provides a kind of new plural gel, and
The plural gel has excellent elasticity and ductility and chemical property；
2) it is extensive, low in cost to prepare raw material sources by the present invention；
3) for preparation method of the present invention without auxiliary agents such as adhesives, integrated artistic environmental protection is succinct, can the production of industrial high efficiency rate；
4) plural gel maintains the structure of original BC gel, has the advantages that high porosity and high-specific surface area；
5) after conductive processing, the chemical property of plural gel can further be strengthened.
Detailed description of the invention
Fig. 1 is the SEM figure and XRD diagram of original BC gel；
Fig. 2 is that the SEM of embodiment 6, embodiment 7 and embodiment 10 schemes；
Fig. 3 is embodiment 6, the XRD diagram of embodiment 7 and embodiment 10；
Fig. 4 is that the SEM of embodiment 11~13 schemes；
Fig. 5 is that the SEM of embodiment 14~16 schemes；
Fig. 6 is that the SEM of obtained BC/CuS plural gel schemes；
Fig. 7 is the XRD diagram and SEM figure of embodiment 20；
Fig. 8 is the XRD diagram and SEM figure of embodiment 27；
Fig. 9 is obtained BC/VS4The XRD diagram and SEM of plural gel are schemed；
Figure 10 is the SEM figure of the BC/ metal sulfide plural gel after conductive processing.
Specific embodiment
Embodiment 1~16
A kind of preparation method of bacteria cellulose/metal sulfide plural gel, the preparation method includes following preparation step:
1) it prepares maceration extract: the soluble-salt containing a kind of metal target ingredient is formulated as maceration extract；
2) load dipping: it will be impregnated in step 1) acquired solution and be carried out at dipping by pretreated bacterial cellulose gel
Reason, makes bacterial cellulose gel carried metal compound particles, obtains intermediate；
3) hydro-thermal process: hydro-thermal process is carried out to the intermediate obtained after step 2) impregnation, obtains plural gel；
4) displacement drying: multiple solvent displacement is carried out to the plural gel obtained after step 3) hydro-thermal process, is subsequently dried
Obtain bacteria cellulose/metal sulfide plural gel.
Wherein, metal contained in bacteria cellulose prepared by Examples 1 to 10/metal sulfide plural gel vulcanizes
Object is nickel sulfide, and metal sulfide prepared by embodiment 11~15 is copper sulfide, and design parameter is as shown in following table table 1.
The specific preparation parameter of 1 embodiment of table 1~16
Wherein, the molar concentration of nickel solution I and nickel solution II are nickel ion molar concentration contained therein, nickel solution I
Nickel source with nickel solution II is soluble nickel salt, including nickel acetate, nickel nitrate, nickel chloride and nickel sulfate.The solution of nickel solution I
System are as follows: water and dimethylformamide are mixed first with the ratio of volume ratio 1:1 when preparation, are added nickel source after mixing, then with
Molar ratio Ni+: thiocarbamide is added in thiocarbamide=1:2 ratio；The solution system of nickel solution II are as follows: first by water and dimethyl when preparation
Formamide is mixed with the ratio of volume ratio 1:1, nickel source is added after mixing, then with molar ratio Ni+:N, the double thions of two sulphur of N- tetramethyl
N, the double thiamides of two sulphur of N- tetramethyl are added in amine=1:0.5 ratio.The condition that 4~5 pairs of maceration extracts of embodiment are compounded is
Maceration extract and ethylene glycol are mixed with the ratio of volume ratio 5:1；The condition that 9~10 pairs of maceration extracts of embodiment are compounded is that will soak
Stain liquid and ethylene glycol are mixed with the ratio of volume ratio 4:1.
Wherein, the molar concentration of copper solution is the molar concentration of copper ion, and the copper source of copper ion is soluble copper salt.Copper is molten
The solution system of liquid is the aqueous solution of soluble copper salt.The organic solution of hydrothermal solution system is the ethylene glycol containing sulphur source.Sulphur
Source includes but are not limited to thiocarbamide, N, one of double thiamides of two sulphur of N- tetramethyl or a variety of mixing, the molar concentration of sulphur
For 1~2mol/L.
Using XRD, SEM, XPS, TG, FTIR and BET etc. to bacteria cellulose obtained by embodiment 1~16/metal sulphur
Compound plural gel is tested and analyzed, and is carried out SEM and XRD to primitive bacteria cellulose gel and detected, testing result such as Fig. 1
As shown in the figure.Wherein, the SEM of embodiment 6,7,10 schemes as shown in Fig. 2, A is embodiment 6 in Fig. 2, B is embodiment 7, C is implementation
Example 10, and with the BC gel SEM figure of Fig. 1 compare then can from figure it will be evident that in Fig. 1 original BC gel have it is abundant
Three-dimensional porous network structure, and bacterial cellulose gel itself has after loading nickel sulfide three-dimensional porous network structure is protected
Hold constant, and nickel sulphide particles are uniformly distributed on bacteria cellulose nanofiber surface, good combination between two kinds of components,
Especially embodiment 7 and embodiment 10 are formed by nickel sulphide particles attachment ten in bacteria cellulose/metal sulfide plural gel
Divide uniformly, has compared to BC gel specific surface area in Fig. 1 and obviously promoted, in addition, embodiment 6, embodiment 7 and embodiment
10 XRD test map is evident that loaded metallic compound is nickel sulfide as shown in Figure 3, and nickel sulfide is received by BC
Uniform load is realized after the effect of great amount of hydroxy group functional group on rice fiber.
Wherein embodiment 11, embodiment 12 and embodiment 13 SEM figure as shown in figure 4, by Fig. 4 it will be evident that its
Nanosphere growth is larger, and increasing with copper ion concentration, and particle is gradually tended to spherical particle simultaneously by irregular shape
Partial size is also increasing, and compared to nickel sulfide, the particle of the copper sulphide nano ball grown in embodiment 11~13 and bacterium are fine
It ties up plain nanofiber generation to tangle, attachment stability is very high, but flexibility to bacterial cellulose gel and porosity will
Generate influence to a certain extent.Variable Control is carried out on the basis of embodiment 11~13 is prepared for 14~embodiment of embodiment
16, the SEM of embodiment 14~16 figure as shown in figure 5, the hydro-thermal time shorten after copper sulphide nano ball uniformity decline, occur
The case where local accumulation is reunited, but make moderate progress after the hydro-thermal time extends in the situation, the preparation process of reference implementation example 14,
Only changing the hydro-thermal time is respectively 12h, 18h and for 24 hours, be can be obtained as shown in Figure 6 as a result, therefore best hydro-thermal time >=12h is
Best hydro-thermal time range.
Again to bacteria cellulose obtained by embodiment 1~16/metal sulfide plural gel and primitive bacteria cellulose
Gel carries out flexibility, porosity and specific surface area, and compares the two shape characteristic, and after loading NiS or CuS, bacterium is fine
The advantages that plain aeroge still keeps high-flexibility, high porosity and high-specific surface area is tieed up, is had clearly in specific surface area
Promotion this is because the nanofiber surface of primitive bacteria cellulose gel is smooth be simple one-dimentional structure fiber,
And after loading sulfide nanoparticle, the great amount of hydroxy group functional group on bacteria cellulose fibre surface and a large amount of holes are metal sulphur
The growth of compound provides high activity region and big surface area.NiS or CuS particle with rough surface is uniformly by bacterium fibre
Cellulose fiber is wound, caused by its specific surface area of further expansion.And the nanosphere that nickel sulfide is grown is tiny, abundant uniform,
Nanosphere rough surface, therefore the promotion of specific surface area is fairly obvious.In addition to this, with addition NiS presoma (i.e. nickel source)
Amount increase, the amount for being fixed on the NiS particle on bacteria cellulose skeleton increases, and also evolves into gradually from rectangular particle in form
Circular granular.Especially in embodiment 10, the uniformity of nickel sulfide (NiS) nanosphere distribution is high.As CuS precursor concentration increases
Greatly, CuS particle is developed from irregular shape to spherical.The hydro-thermal reaction time is discussed to compound in the case where mantoquita concentration is 0.3M
The influence of material, finds hydro-thermal reaction 12h, 18h, for 24 hours as shown in Figure 6, CuS particle be it is spherical, only with the reaction time
Lengthening, granular size and distribution it is more and more uniform.
Embodiment 17~19
Specific preparation parameter, step are identical as embodiment 11, and difference is: maceration extract heats the metavanadic acid of 2h under the conditions of being 70 DEG C
Aqueous ammonium, wherein the concentration of ammonium metavanadate is respectively 0.10mol/L, 0.12mol/L and 0.15mol/L, hydrothermal solution system
Ethylene glycol solution from isometric 0.6mol/L thioacetamide is added into maceration extract is compounded to obtain.Products therefrom is thin
Fungin/vanadic sulfide plural gel.
Embodiment 20~28
A kind of preparation method of bacteria cellulose/metal sulfide plural gel, the preparation method includes following preparation step:
1) it prepares maceration extract: the soluble metallic salt dissolution containing Determination of multiple metal elements is formulated as maceration extract；
2) load dipping: it will be impregnated in step 1) acquired solution and be carried out at dipping by pretreated bacterial cellulose gel
Reason, makes bacterial cellulose gel carried metal compound particles, obtains intermediate；
3) hydro-thermal process: hydro-thermal process is carried out to the intermediate obtained after step 2) impregnation, obtains plural gel；
4) displacement drying: carrying out the displacement of three-step approach solvent to the plural gel obtained after step 3) hydro-thermal process, specific
Process are as follows: sequentially successively plural gel is impregnated using water, ethyl alcohol and the tert-butyl alcohol.Then freeze-drying obtains bacterial fibers
Element/metal sulfide plural gel.
Its specific preparation parameter is as shown in following table table 2 and table 3.
2 preparation parameter Table I of table
3 preparation parameter Table II of table
Using XRD, SEM, XPS, TG, FTIR and BET etc. to bacteria cellulose obtained by embodiment 20~28/metal sulphur
Compound plural gel is detected, and wherein the XRD diagram of 20 gained BC/Ni-Co-S gel of embodiment and SEM figure are as shown in fig. 7, real
27 gained BC/Ni-V-S gel XRD diagram of example and SEM figure are applied as shown in figure 8, simultaneously replacing maceration extract referring to the step of embodiment 27
It is the 0.12mol/L ammonium metavanadate solution for keeping the temperature 2h at 70 DEG C, prepares BC/VS4Gel, SEM figure and XRD diagram as shown in figure 9,
Fig. 8 and Fig. 9 is compared with the XRD diagram of primitive bacteria cellulose gel shown in Fig. 1 and SEM figure, finds impurity on its products obtained therefrom
Content is extremely low, maintains the high levels of three-dimensional network structure of indigenous bacteria cellulose, has great specific surface area.
In addition, 112 samples are prepared on the basis of Examples 1 to 28, it is compound to bacteria cellulose/metal sulfide solidifying
Glue carries out conductive treatment.The step of wherein 28 samples use carbonization treatment, carbonization treatment are as follows: pretreated matrix will be passed through
Bacterial cellulose gel in protective atmosphere with the heating rate of 3~5 DEG C/min be warming up to 230~280 DEG C and keep the temperature 1.5~
3h is then warming up to 550~620 DEG C again with the heating rate of 3~5 DEG C/min and keeps the temperature 1.5~3h furnace cooling, remaining step
It is corresponding with Examples 1 to 28 respectively；The step of other 28 samples carry out the processing of PPy cladding, and PPy cladding is handled are as follows: by water
The plural gel obtained after heat is placed in pyrroles's aqueous solution of 1mol/L and stirs, and equivalent 0.5mol/L iron chloride is then slowly added dropwise
Solution reacts 1.5~3h under the conditions of -5~2 DEG C after being added dropwise to complete, then repeatedly clear with a large amount of dehydrated alcohols and deionized water
It washes, it is corresponding with Examples 1 to 28 respectively to be finally putting into cleaning 40min, remaining step in the hydrochloric acid of 1mol/L；56 are taken again
The step of a sample carries out polyaniline-coated processing, and polyaniline-coated is handled are as follows: pretreated matrix BC gel or water will be passed through
The plural gel obtained after heat is placed in the aniline monomer solution of 0.5~2mol/L and is carried out at a slow speed with the revolving speed of 20~100r/min
25~35min is stirred, oxidant ammonium persulfate is then added and carries out 2~4h of in-situ polymerization, remaining step and Examples 1 to 28
Preparation step is identical.Subsequent resulting 112 samples are detected.The wherein bacterial fibers that PPy coated with conductive is handled
As shown in Figure 10, structure keeps very complete to element/metal sulfide plural gel SEM figure, has three-dimensional porous network knot
Structure.Testing result show obtained bacteria cellulose/metal sulfide plural gel flexibility after carbonization have 5%~
The decline of 20% degree, but it is essentially identical with 1~28 result of above-described embodiment in terms of the porosity and in terms of specific surface area；Poly- pyrrole
Resulting bacteria cellulose/metal sulfide plural gel is in terms of flexibility, porosity and specific surface area after coughing up cladding processing
Etc. it is essentially identical with 1~28 result of above-described embodiment；Resulting bacteria cellulose/metal sulphur after polyaniline-coated processing
Compound plural gel in terms of flexibility, porosity and in terms of with the basic phase of 1~28 result of above-described embodiment
Together.Also, the electric conductivity of sample is significantly promoted after carbonization treatment or after the processing of polypyrrole cladding or polyaniline-coated processing,
With good conductive effect.The sample electric conductivity that wherein processing of PPy cladding and polyaniline-coated obtain after handling is better than carbon
Change treated sample, carbonization treatment cost lower than the processing of polypyrrole cladding and polyaniline-coated processing, but the above cost compared with
It is low, be applicable to mass production, electric conductivity is promoted fairly obvious.
More than, content can obtain based on the above embodiments: can be prepared by the method for the invention various bacteria cellulose/
Metal sulfide plural gel, and raw material sources are extensive, low in cost, it is whole without auxiliary agents such as adhesives in preparation process
It is environmental friendly succinct, can the production of industrial high efficiency rate, obtained plural gel maintains the structure of original BC gel, has height
The advantages of porosity and high-specific surface area, after conductive processing, the chemical property of plural gel can further be strengthened.
Claims (9)
1. a kind of bacteria cellulose/metal sulfide plural gel preparation method, which is characterized in that the preparation method includes
Following preparation step:
1) it prepares maceration extract: the dissolution of one or more salt is formulated as maceration extract；
2) load dipping: pretreated bacterial cellulose gel is impregnated in maceration extract obtained by step 1) and is carried out at dipping
Reason；
3) hydro-thermal process: the bacterial cellulose gel through step 2) impregnation is put into the solution of sulfur-bearing and is carried out at hydro-thermal
Reason, obtains plural gel；
4) displacement drying: carrying out multiple solvent displacement to the plural gel through step 3) hydro-thermal process, be then dried, dry
After obtain bacteria cellulose/multi-element metal sulfide plural gel,
Wherein, containing at least one metal target element in the step 1) maceration extract, the metal target element include iron,
Vanadium, nickel, copper, cobalt and rhenium.
2. a kind of preparation method of bacteria cellulose/metal sulfide plural gel according to claim 1, feature exist
In the preprocessing process of the step 2) bacterial cellulose gel is to impregnate bacterial cellulose gel simultaneously using sodium hydroxide solution
Washing is to neutrality, the when a length of 8~16h for being placed in impregnation in maceration extract.
3. a kind of preparation method of bacteria cellulose/metal sulfide plural gel according to claim 1, feature exist
A length of 3 when, the step 3) hydro-thermal process~for 24 hours, solution used in hydro-thermal process is maceration extract, step 1) institute obtained by step 1)
Obtain the combination solution or organic solution of maceration extract.
4. a kind of preparation method of bacteria cellulose/metal sulfide plural gel according to claim 1, feature exist
In the step 4) solvent is replaced into the displacement of three-step approach solvent, detailed process are as follows: sequentially successively utilizes water, ethyl alcohol and tertiary fourth
Alcohol impregnates plural gel.
5. a kind of preparation method of bacteria cellulose/metal sulfide plural gel according to claim 1 or 4, special
Sign is that step 4) is described dry using freeze-drying.
6. a kind of bacteria cellulose as made from claims 1 to 5 any one the method/metal sulfide plural gel,
It is characterized in that, the bacteria cellulose/metal sulfide plural gel is the gel with high porosity and high-specific surface area
Shape, matrix are the bacterial cellulose gel containing three-dimensional porous network structure, and doping contains inside the three-dimensional porous structure
Metal sulfide grain.
7. a kind of bacteria cellulose/metal sulfide plural gel according to claim 6, which is characterized in that the gold
Category sulfide grain is spheric granules.
8. one kind is for bacteria cellulose/metal sulfide plural gel made from claim 1 to 5 any one the method
Conductive processing method, which is characterized in that the conductive processing method be carbonization treatment or polypyrrole cladding processing or polyaniline
Cladding processing.
9. it is according to claim 8 a kind of for bacteria cellulose/metal sulfide plural gel conductive processing method,
It is characterized in that, the step of carbonization treatment are as follows: will add in protective atmosphere by pretreated bacterial cellulose gel
Heat is to 230~280 DEG C and keeps the temperature 1.5~3h, then raise temperature to 550~620 DEG C and keeps the temperature 1.5~3h furnace cooling；It is described poly-
Pyrroles coats the step of processing are as follows: the plural gel obtained after hydro-thermal is placed in pyrroles's aqueous solution and is stirred, is then slowly added dropwise
Equivalent ferric chloride solution reacts 1.5~3h under the conditions of -5~2 DEG C after being added dropwise to complete；The step of polyaniline-coated processing
Are as follows: the plural gel obtained after pretreated bacterial cellulose gel or hydro-thermal is placed in aniline monomer solution and is stirred,
Oxidant is then added and carries out 2~4h of in-situ polymerization.
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