CN109961962A - Load the preparation method of the galapectite electrode material of Ni, Mn oxide and curing nickel - Google Patents
Load the preparation method of the galapectite electrode material of Ni, Mn oxide and curing nickel Download PDFInfo
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- CN109961962A CN109961962A CN201711425420.4A CN201711425420A CN109961962A CN 109961962 A CN109961962 A CN 109961962A CN 201711425420 A CN201711425420 A CN 201711425420A CN 109961962 A CN109961962 A CN 109961962A
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- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/46—Metal oxides
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Abstract
The invention discloses the preparation methods of a kind of load Ni, Mn oxide and the galapectite electrode material of curing nickel.Using halloysite nanotubes as template, natural halloysite nanotubes after pretreatment, handle its surface and its inner cavity to obtain the galapectite of carboxyl modified the method using silane resin acceptor kh-550, succinic anhydride respectively.Then the galapectite of six water nickel chlorides, four water manganese acetates and carboxyl modified is dissolved in deionized water, methenamine and sodium citrate is uniformly added in ultrasonic disperse afterwards, Ni, Mn oxide is loaded using hydro-thermal reaction, obtains Ni, Mn oxide/carboxyl halloysite composite material.Finally, passing through vulcanization reaction in sodium sulfide solution, two steps synthesize curing nickel/Ni, Mn oxide/galapectite active material.Composite material specific capacitance with higher produced by the present invention, and cost is relatively low, reaction is mild, it is easily prepared, great application prospect is presented in energy storage field.
Description
Technical field
The invention belongs to electrode material preparation technical fields, and in particular to a kind of load Ni, Mn oxide and curing nickel
The preparation method of galapectite electrode material.
Background technique
Supercapacitor has high power density and excellent cycling stability, as the energy stores in new energy development
Switching device is with a wide range of applications.The chemical property of supercapacitor depends primarily on electrode material and electrolyte.
Therefore, new and effective electrochemical energy storage materials are researched and developed to be of great significance to the chemical property for effectively improving supercapacitor
(①Steven Chu,Arun Majumdar.Opportunities and challenges for a sustainable
energy future.Nature,2012,488,294-303.)。
Transient metal sulfide, such as CoS, NiS, CuS, MoS2Deng with its unique physics with chemical property (as compared carbon
Material has high electric conductivity, has than metal oxide with higher thermal stability), and facilitate the richness of height ratio capacity
Redox reaction is shown one's talent as electrochemical active material.Xiao etc. is prepared for using electrochemical deposition method with tubulose
The NiCo of structure2S4, 4mA cm-2Current density under, specific capacity be 0.87F cm-2, current density is 20mA cm-2When, specific volume
Amount is 0.58F g-1.Electroactive material CoxNi1-x(OH)2It is introduced for preparation CoxNi1-x(OH)2/NiCo2S4Composite material, electricity
Chemical property has been significantly improved, 4mA cm-2Current density under, specific capacity is up to 2.86F cm-2, current density is
20mA cm-2When, specific capacity is up to 2.41F g-1。(②Xin Yao Yu,et al.Metal sulfide hollow
nanostructures for electrochemical energy storage.Advanced Energy Materials,
2016,6,1501333.；③Junwu Xiao,et al.Design hierarchical electrodes with highly
conductive NiCo2S4nanotube arrays grown on carbon fiber paper for high-
performance pseudocapacitors.Nano letters,2014,14,831-838.)。
Galapectite is crimped under natural endowment by kaolinic lamella, is mainly present in the form of nanotube-shaped
In nature.Galapectite lays in hollow tubular material abundant as a kind of naturally, the length is 0.5-1 μm, outer diameter 50-
70nm, internal diameter are about 15nm, and specific surface area and porosity is big, advantageously form bigger electric double layer capacitance, the negative electrical charge on surface
It is more advantageous to the load of transition metal oxide or sulfide, compared with carbon nanotube, cost is lower and pollution-free.In addition, angstrom
The inner wall of Lip river madreporic canal is Al-OH group, and pipe outer wall exists in the form of O-Si-O group, and this special inside and outside unit structure makes
It possesses wider array of application range and richer inquiry.Liang etc. is by the mild precipitation method, by nano-sheet
NiCo2O4It is grown in halloysite nanotubes surface.Due to halloysite nanotubes promote the diffusion of anion/cation in electrolyte with
And ultra-thin NiCo2O4Nanometer sheet, so that NiCo2O4/ halloysite composite material has high specific capacitance and excellent stable circulation
Property.Test result shows that under the current density of 10A/g, the specific capacitance of this composite material has reached 1728F/g, by 8600
Capacity retention ratio 94.7% after secondary charge and discharge cycles, better than other commercial activated Carbon Materials.(④Jin Liang,et
al.Hierarchical NiCo2O4nanosheets@halloysite nanotubes with ultrahigh
capacitance and long cycle stability as electrochemical pseudocapacitor
materials.Chemistry of Materials,2014,26,4354-4360.；⑤Ravindra Kamble,et
al.Halloysite Nanotubes and Applications:A Review.Journal of Advanced
Scientific Research,2012,3,25-29.)
Summary of the invention
The present invention provides the galapectite electrode material of a kind of synthesis of two step of hydro-thermal method load Ni, Mn oxide and curing nickel
Preparation method.
The technical solution of the present invention is as follows:
Load the preparation method of the galapectite electrode material of Ni, Mn oxide and curing nickel, the specific steps are as follows:
Step 1, by natural halloysite nanotubes, ultrasonic disperse, standing take upper suspension simultaneously in Sodium Meta Hexa Phosphate 62 and 67 P2O5 contents solution
With water eccentric cleaning, vacuum drying obtains halloysite nanotubes；
Step 2, silane resin acceptor kh-550 and halloysite nanotubes are dispersed in toluene, under nitrogen protection, reflux is anti-
It answers, obtains amido modified halloysite nanotubes after washing is dry, then by succinic anhydride and dry amido modified galapectite
Nanotube is dispersed in N-N- dimethylformamide (DMF), washing and drying after stirring, obtains the galapectite nanometer of carboxyl modified
Pipe；
Step 3, the halloysite nanotubes of six water nickel chlorides, four water manganese acetates and carboxyl modified are dissolved in water,
Ultrasonic treatment, wherein the concentration of the galapectite of carboxyl modified is 1~4mg/mL；
Step 4, four water manganese acetates, sodium citrate are separately added into the mixed solution that step 3 obtains, after ultrasound is uniform,
6~8h of agitating and heating at 80~90 DEG C is centrifuged after reaction, washs, is dry, obtaining Ni, Mn oxide/carboxyl galapectite
Electrode material, wherein the molar concentration rate of methenamine solution and four water acetic acid manganese solutions is 4~14:1；
Step 5, Ni, Mn oxide/carboxyl galapectite is dispersed in sodium sulfide solution, after mixing evenly, 160~
It is reacted at 180 DEG C 6~8 hours, is centrifuged, washs after reaction, is dry, obtaining curing nickel/nickel-manganese-oxygen of hollow structure
Object/carboxyl galapectite electrode material.
Preferably, in step 2, reflux time be for 24 hours more than；The mass ratio of galapectite and silane resin acceptor kh-550
For 1:2；The mass ratio of succinic anhydride and amido modified halloysite nanotubes is 0.6:1.
Preferably, in step 3, it is ultrasonically treated 30~40min；The galapectite concentration of carboxyl modified is 2mg/mL.
Preferably, in step 4, the molar concentration rate of methenamine solution and four water acetic acid manganese solutions is 8:1；Methenamine
The molar concentration rate of solution and sodium citrate solution is 10:1.
Preferably, in step 5, vulcanized sodium and Ni, Mn oxide/carboxyl galapectite mass ratio are 1:1.5.
Compared with prior art, the present invention its remarkable advantage is as follows: (1) raw material is cheap and easy to get, convieniently synthesized, reaction is warm
It is good and controllable with crystal form；(2) it is easier to combine metal cation through KH-550, the processed galapectite of succinic anhydride, is conducive to nickel
Mn oxide is grown on halloysite nanotubes surface；(3) using the galapectite of high-specific surface area as two sulphur of base load
Change nickel, improve the crystallinity of three nickel of curing, increase the contact area with electrolyte, is provided for ion diffusion more
Channel；(4) the curing nickel/Ni, Mn oxide/halloysite composite material prepared shows very high under the current density of 1A/g
Specific capacitance (2610F/g), and have excellent stability, capacity retention ratio is after 2000 charge and discharge cycles
92.6%.
Detailed description of the invention
Fig. 1 is curing nickel/Ni, Mn oxide/carboxyl halloysite composite material preparation method schematic diagram.
Fig. 2 is curing nickel/Ni, Mn oxide/carboxyl halloysite composite material X-ray diffractogram.
Fig. 3 is curing nickel/Ni, Mn oxide/carboxyl halloysite composite material transmission electron microscope picture.
Fig. 4 is curing nickel/Ni, Mn oxide/cyclic voltammetric of the carboxyl halloysite composite material under different scanning speed
Curve.
Fig. 5 is that electric discharge of the curing nickel/Ni, Mn oxide/carboxyl halloysite composite material under different current densities is bent
Line.
Fig. 6 is Ni, Mn oxide, Ni, Mn oxide/carboxyl galapectite, curing nickel/Ni, Mn oxide, curing nickel/nickel
Mn oxide/discharge curve of the carboxyl galapectite under 1A/g current density.
Fig. 7 is Ni, Mn oxide, Ni, Mn oxide/carboxyl galapectite, curing nickel/Ni, Mn oxide, curing nickel/nickel
Mn oxide/carboxyl halloysite composite material specific capacitance decay pattern.
Specific embodiment
Below with reference to embodiment and attached drawing, present invention is further described in detail.
In conjunction with attached drawing 1, the present invention prepares the side of curing nickel hollow structure electrode material using halloysite nanotubes as template
Method, steps are as follows:
The first step pre-processes natural halloysite nanotubes using Sodium Meta Hexa Phosphate 62 and 67 P2O5 contents, removes the Ai Luo for being easy to reunite
Stone nanotube；
Second step is first modified halloysite nanotubes surface using silane resin acceptor kh-550, reacts at 120 DEG C
For 24 hours, amido modified halloysite nanotubes are obtained, recycles succinic anhydride to handle amination galapectite, obtains carboxyl modified
Halloysite nanotubes；
The galapectite of six water nickel chlorides, four water manganese acetates and carboxyl modified is dissolved separately in deionized water by third step,
It is ultrasonically treated 30~40min；
Methenamine and sodium citrate are separately added into the mixed solution that third step obtains by the 4th step, after ultrasound is uniform
Mixture is transferred in round-bottomed flask, the agitating and heating 6h at 90 DEG C；
Product after reaction is centrifuged by the 5th step, is washed respectively for several times with water and ethyl alcohol, obtains nickel-manganese-oxygen after dry
Object/carboxyl halloysite composite material.
6th step, the Ni, Mn oxide that the 5th step is obtained/carboxyl halloysite composite material ultrasonic disperse is in deionized water
In, vulcanized sodium is added, suspension is transferred in autoclave after stirring 30min.
7th step, after 160 DEG C are reacted 8 hours, black precipitate is centrifuged by natural cooling, is washed respectively with water and ethyl alcohol
For several times, curing nickel/Ni, Mn oxide/carboxyl halloysite composite material is obtained after drying.
Three nickel composite material preparation method of sulfydryl galapectite/curing of the present invention, technical conditions are as follows: natural galapectite and partially
The mass ratio of sodium hexametaphosphate is 1:0.005, and the mass ratio of galapectite and KH-550 are 1:2；Succinic anhydride and amination galapectite
Mass ratio be 0.6:1；The galapectite concentration of carboxyl modified is 1mg/mL, 2mg/mL, 3mg/mL, 4mg；Four water acetic acid manganese solutions
Concentration be 0.01M, the molar concentration rate of six water nickel chloride solutions and four water acetic acid manganese solutions is 3:1；Methenamine solution with
The molar concentration rate of four water acetic acid manganese solutions is 8:1, and the molar concentration rate of methenamine solution and sodium citrate solution is 10:1；
The mass ratio of Ni, Mn oxide/carboxyl galapectite and vulcanized sodium is 1.5:1.
Embodiment 1
Load the preparation method of the galapectite electrode material of Ni, Mn oxide and curing nickel, comprising the following steps:
The first step, by the mixed solution ultrasound of Sodium Meta Hexa Phosphate 62 and 67 P2O5 contents (0.05wt%) and natural halloysite nanotubes (10wt%)
20min is stood after 30min, takes supernatant liquid, three times with water centrifuge washing, is dried in vacuo 6h at 50 DEG C；
Second step takes dry toluene (10mL), and 70mL KH-550 and pretreated halloysite nanotubes are added
(3g), for 24 hours, for several times with toluene and ethanol washing, vacuum temperature dries 8h to the lower 120 DEG C of reactions of nitrogen atmosphere at 40 DEG C, obtains amino
The galapectite of modification；The succinic anhydride and HNT-NH of 0.6g2(1g) is dissolved into the DMF of 60mL, and stirring is centrifuged after one day with water
Washing, vacuum drying (40 DEG C/8h), finally obtain carboxyl galapectite.
60mg carboxyl galapectite is dispersed in 60mL water by third step, and six water nickel chlorides (1.8mmol) and four are then added
Water manganese acetate (0.6mmol) is ultrasonically treated 30min；
4th step, by methenamine (4.8mmol) and sodium citrate (0.24mmol) be separately added into that third step obtains it is mixed
It closes in solution, is transferred into round-bottomed flask after ultrasound is uniform, the agitating and heating 6h at 90 DEG C；
Product after reaction is centrifuged by the 5th step, is washed respectively for several times with water and ethyl alcohol, obtains nickel-manganese-oxygen after dry
Object/carboxyl halloysite composite material.As electrode material for super capacitor, the specific capacitance under the current density of 1A/g is for it
1357.4F/g。
Embodiment 2
The additional amount of carboxyl galapectite is 120mg in third step unlike the present embodiment and embodiment 1 are unique, other with
Embodiment 1 is identical.The Ni, Mn oxide prepared/carboxyl halloysite composite material is as electrode material for super capacitor in 1A/g
Current density under specific capacitance be 1496.3F/g, specific capacitance retention rate is 52.3% under 20A/g current density.
Embodiment 3
The additional amount of carboxyl galapectite is 180mg in third step unlike the present embodiment and embodiment 1 are unique, other with
Embodiment 1 is identical.The Ni, Mn oxide prepared/carboxyl halloysite composite material is as electrode material for super capacitor in 1A/g
Current density under specific capacitance be 1255.2F/g.
Embodiment 4
The additional amount of carboxyl galapectite is 240mg in third step unlike the present embodiment and embodiment 1 are unique, other with
Embodiment 1 is identical.The Ni, Mn oxide prepared/carboxyl halloysite composite material is as electrode material for super capacitor in 1A/g
Current density under specific capacitance be 1135.9F/g.
Embodiment 5
Six water nickel chloride (1.8mmol) He Sishui manganese acetates (0.6mmol) are dissolved in 60mL water by the first step, ultrasound
Handle 30min；
Second step, by methenamine (4.8mmol) and sodium citrate (0.24mmol) be separately added into that second step obtains it is mixed
It closes in solution, is transferred into round-bottomed flask after ultrasound is uniform, the agitating and heating 6h at 90 DEG C；
Product after reaction is centrifuged by third step, is washed respectively for several times with water and ethyl alcohol, obtains nickel-manganese-oxygen after dry
Object.The Ni, Mn oxide prepared/electric current of the carboxyl halloysite composite material as electrode material for super capacitor in 1A/g is close
Spending lower specific capacitance is 1212.6F/g, and specific capacitance retention rate is 43.6% under 20A/g current density.
Embodiment 6
Load the preparation method of the galapectite electrode material of Ni, Mn oxide and curing nickel, comprising the following steps:
The first step, by the mixed solution ultrasound of Sodium Meta Hexa Phosphate 62 and 67 P2O5 contents (0.05wt%) and natural halloysite nanotubes (10wt%)
20min is stood after 30min, takes supernatant liquid, three times with water centrifuge washing, is dried in vacuo 6h at 50 DEG C；
Second step takes dry toluene (10mL), and 70mL KH-550 and pretreated halloysite nanotubes are added
(3g), for 24 hours, for several times with toluene and ethanol washing, vacuum temperature dries 8h to the lower 120 DEG C of reactions of nitrogen atmosphere at 40 DEG C, obtains amino
The galapectite of modification；The succinic anhydride and HNT-NH of 0.6g2(1g) is dissolved into the DMF of 60mL, and stirring is centrifuged after one day with water
Washing, vacuum drying (40 DEG C/8h), finally obtain carboxyl galapectite.
60mg carboxyl galapectite is dispersed in 60mL water by third step, and six water nickel chlorides (1.8mmol) and four are then added
Water manganese acetate (0.6mmol) is ultrasonically treated 30min；
4th step, by methenamine (4.8mmol) and sodium citrate (0.24mmol) be separately added into that third step obtains it is mixed
It closes in solution, is transferred into round-bottomed flask after ultrasound is uniform, the agitating and heating 6h at 90 DEG C；
Product after reaction is centrifuged by the 5th step, is washed respectively for several times with water and ethyl alcohol, obtains nickel-manganese-oxygen after dry
Object/carboxyl halloysite composite material.
6th step exists Ni, Mn oxide/carboxyl halloysite composite material (300mg) ultrasonic disperse that the 5th step obtains
It in 60mL deionized water, is added vulcanized sodium (200mg), suspension is transferred in autoclave after stirring 30min, 160
DEG C after reaction 8 hours, black precipitate is centrifuged by natural cooling, is washed respectively for several times with water and ethyl alcohol, obtains two sulphur after dry
Change nickel/Ni, Mn oxide/carboxyl halloysite composite material.It is as electrode material for super capacitor under the current density of 1A/g
Specific capacitance is 2610F/g, and specific capacitance retention rate is 63% under 20A/g current density.
Embodiment 7
Six water nickel chloride (1.8mmol) He Sishui manganese acetates (0.6mmol) are dissolved in 60mL water by the first step, ultrasound
Handle 30min；
Second step, by methenamine (4.8mmol) and sodium citrate (0.24mmol) be separately added into that second step obtains it is mixed
It closes in solution, is transferred into round-bottomed flask after ultrasound is uniform, the agitating and heating 6h at 90 DEG C；
Product after reaction is centrifuged by third step, is washed respectively for several times with water and ethyl alcohol, obtains nickel-manganese-oxygen after dry
Object.
Vulcanized sodium is added in 60mL deionized water in 4th step, the Ni, Mn oxide ultrasonic disperse that third step is obtained
Suspension is transferred in autoclave by (200mg) after stirring 30min, and after 160 DEG C are reacted 8 hours, natural cooling will
Black precipitate centrifugation, is washed for several times respectively with water and ethyl alcohol, obtains curing nickel/Ni, Mn oxide composite material after dry.
As electrode material for super capacitor, the specific capacitance under the current density of 1A/g is 2535.6F/g for it, is compared under 20A/g current density
Capacitor retention rate is 34.7%.
Fig. 2 is curing nickel/Ni, Mn oxide/carboxyl halloysite composite material scanning electron microscope (SEM) photograph.Wherein, (a) carboxyl
The scanning electron microscope (SEM) photograph of galapectite, (b) curing nickel/Ni, Mn oxide/carboxyl galapectite scanning electron microscope (SEM) photograph, two figures of comparison can be with
Find out, the surface of galapectite becomes coarse from smooth, it was demonstrated that the successful load of curing nickel and Ni, Mn oxide.
Fig. 3 is curing nickel/Ni, Mn oxide/carboxyl halloysite composite material transmission electron microscope picture.Wherein, (a) carboxyl
The transmission electron microscope picture of galapectite, (b) curing nickel/Ni, Mn oxide/carboxyl galapectite transmission electron microscope picture, the comparison of Cong Liangtu
In as can be seen that the surface of galapectite becomes coarse from smooth, surface is wrapped in cake mass, it was demonstrated that three nickel of curing at
Function load.
Fig. 4 is curing nickel/Ni, Mn oxide/cyclic voltammetric of the carboxyl halloysite composite material under different scanning speed
Curve.Test electrode is three-electrode system, and composite material and associated materials are assembled into working electrode, is opposed electricity with platinum electrode
Pole, saturated calomel electrode (SCE) make reference electrode, and electrolyte is 2M KOH.
Fig. 5 is that electric discharge of the curing nickel/Ni, Mn oxide/carboxyl halloysite composite material under different current densities is bent
Line.Pass through formula Cs=I* Δ t/ (m* Δ V) can calculate specific capacitance (C of the electrode material under 1A/g current densitys) be
2610F/g。
Note: the 1) galapectite after above-mentioned carboxyl galapectite Dai Zhiyong carboxyl modified.
2) in above-mentioned formula, I is discharge current, and Δ t is discharge time, and m is active material quality, and Δ V is voltage range.
Fig. 6 is Ni, Mn oxide, Ni, Mn oxide/carboxyl galapectite, curing nickel/Ni, Mn oxide, curing nickel/nickel
Mn oxide/discharge curve of the carboxyl galapectite under 1A/g current density.Wherein curing nickel/Ni, Mn oxide/carboxyl angstrom
The discharge time longest of Lip river stone composite material, corresponding specific capacitance are maximum.
Fig. 7 is Ni, Mn oxide, Ni, Mn oxide/carboxyl galapectite, curing nickel/Ni, Mn oxide, curing nickel/nickel
Mn oxide/carboxyl halloysite composite material specific capacitance decay pattern.Wherein, curing nickel/Ni, Mn oxide/carboxyl galapectite
Specific capacitance of the composite material under 1A/g current density is maximum (2610F/g), the specific capacitance retention rate under 20A/g current density
Highest (63%).
Claims (5)
1. loading the preparation method of the galapectite electrode material of Ni, Mn oxide and curing nickel, which is characterized in that specific steps
It is as follows:
Step 1, by natural halloysite nanotubes, ultrasonic disperse, standing take upper suspension and use water in Sodium Meta Hexa Phosphate 62 and 67 P2O5 contents solution
Eccentric cleaning, vacuum drying obtain halloysite nanotubes；
Step 2, silane resin acceptor kh-550 and halloysite nanotubes are dispersed in toluene, under nitrogen protection, back flow reaction is washed
Wash it is dry after obtain amido modified halloysite nanotubes, then by succinic anhydride and dry amido modified halloysite nanotubes
It is dispersed in N-N- dimethylformamide, washing and drying after stirring obtains the halloysite nanotubes of carboxyl modified；
Step 3, the halloysite nanotubes of six water nickel chlorides, four water manganese acetates and carboxyl modified are dissolved in water, ultrasound
Processing, wherein the concentration of the galapectite of carboxyl modified is 1~4mg/mL；
Step 4, four water manganese acetates, sodium citrate are separately added into the mixed solution that step 3 obtains, after ultrasound is uniform, 80
6~8h of agitating and heating at~90 DEG C is centrifuged after reaction, washs, is dry, obtaining Ni, Mn oxide/carboxyl galapectite electrode
Material, wherein 4~14:1 of molar concentration rate of methenamine solution and four water acetic acid manganese solutions；
Step 5, Ni, Mn oxide/carboxyl galapectite is dispersed in sodium sulfide solution, after mixing evenly, at 160~180 DEG C
Lower reaction 6~8 hours is centrifuged after reaction, washs, is dry, obtaining curing nickel/Ni, Mn oxide/carboxylic of hollow structure
Base galapectite electrode material.
2. preparation method according to claim 1, which is characterized in that in step 2, reflux time be for 24 hours more than；Angstrom
The mass ratio of Lip river stone and silane resin acceptor kh-550 is 1:2；The mass ratio of succinic anhydride and amido modified halloysite nanotubes
For 0.6:1.
3. preparation method according to claim 1, which is characterized in that in step 3, be ultrasonically treated 30~40min；Carboxyl is repaired
The galapectite concentration of decorations is 2mg/mL.
4. preparation method according to claim 1, which is characterized in that in step 4, methenamine solution and four water manganese acetates
The molar concentration rate of solution is 8:1；The molar concentration rate of methenamine solution and sodium citrate solution is 10:1.
5. preparation method according to claim 1, which is characterized in that in step 5, vulcanized sodium and Ni, Mn oxide/carboxyl
The mass ratio of galapectite is 1:1.5.
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| CN111233362A (en) * | 2020-03-25 | 2020-06-05 | 福建江夏学院 | Preparation method and application of concrete toughening material |
| CN111986931A (en) * | 2020-07-24 | 2020-11-24 | 华南理工大学 | Manganese oxide nano-structure electrode material and preparation method and application thereof |
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| CN110534742A (en) * | 2019-07-16 | 2019-12-03 | 江汉大学 | A kind of preparation method of anode composite material of lithium sulfur battery |
| CN110534742B (en) * | 2019-07-16 | 2021-05-28 | 江汉大学 | Preparation method of lithium-sulfur battery positive electrode composite material |
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| CN110776020B (en) * | 2019-11-20 | 2022-01-21 | 江苏师范大学 | NiMnO of stick equipment3Method for synthesizing nanoflower |
| CN111233362A (en) * | 2020-03-25 | 2020-06-05 | 福建江夏学院 | Preparation method and application of concrete toughening material |
| CN111986931A (en) * | 2020-07-24 | 2020-11-24 | 华南理工大学 | Manganese oxide nano-structure electrode material and preparation method and application thereof |
| CN113603106A (en) * | 2021-09-01 | 2021-11-05 | 南京大学 | Method for preparing manganese silicate nanoenzyme based on silicate dissolution kinetics and application |
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