CN106252661A - Bismuth sulfide/carbon nano tube compound material and its preparation method and application - Google Patents
Bismuth sulfide/carbon nano tube compound material and its preparation method and application Download PDFInfo
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- CN106252661A CN106252661A CN201610898199.3A CN201610898199A CN106252661A CN 106252661 A CN106252661 A CN 106252661A CN 201610898199 A CN201610898199 A CN 201610898199A CN 106252661 A CN106252661 A CN 106252661A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1397—Processes of manufacture of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/581—Chalcogenides or intercalation compounds thereof
- H01M4/5815—Sulfides
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention belongs to technical field of composite materials, be specifically related to a kind of bismuth sulfide/carbon nano tube compound material and preparation method thereof and it is as the application in anode material for lithium-ion batteries.Bismuth sulfide/carbon nano tube compound material is meso-hole structure, and wherein the mass ratio of bismuth sulfide/CNT is 1:0.11～0.12, and specific surface area is 65～70cm3/ g, aperture is 3～4nm；Described bismuth sulfide is nano bar-shape structure, a length of 50～150nm, and width is 5～10nm, is wrapped in around CNT；Described CNT plays the bar-shaped Bi of connection2S3Function served as bridge, and at Bi2S3Scope outside surface has extended.The present invention solves bismuth sulfide material at Li+The problem producing volumetric expansion during deintercalation, improves the cycle performance of battery.
Description
Technical field
The invention belongs to technical field of composite materials, be specifically related to a kind of bismuth sulfide/carbon nano tube compound material and system thereof
Preparation Method and its as the application in anode material for lithium-ion batteries.
Background technology
Bi2S3Because specific capacity is high, nature rich reserves and cheap and easy to get, at new type lithium ion battery electrode material
Aspect shows huge potentiality.Various ripe preparation methoies, for Bi2S3Pattern and structure regulating provide good
Basis.Material with carbon element is utilized to modify Bi2S3, Bi can be further enhanced2S3Feasibility as lithium ion battery new electrode materials.
And develop the new electrode materials that height ratio capacity, long-life and high rate performance are excellent, lithium ion battery can be promoted in electric motor car
With the application in terms of portable electric appts, reach alleviating energy crisis, energy security and environmental pollution and greenhouse effect institute
The purpose of the adverse effect brought, really realizes the sustainable development of environmental conservation and the energy.
But, Bi2S3The volume of electrode material can increase by 90% in alloy reaction, and can remove alloy reaction later
Middle continuation increase by 74%, this will be greatly lowered Bi2S3Application potential as electrode material.It would therefore be highly desirable to need a kind of permissible
By distinct methods and material to simple Bi2S3It is modified, reduces it at Li+The volumetric expansion produced during deintercalation, to improve it
The material of cycle performance and method.
Summary of the invention
First technical problem to be solved by this invention is to provide one and is possible to prevent bismuth sulfide material in electrode reaction
During the bismuth sulfide/carbon nano tube compound material of volumetric expansion.
Bismuth sulfide/carbon nano tube compound material, this composite is meso-hole structure, the wherein matter of bismuth sulfide/CNT
Amount ratio is 1:0.11～0.12, and specific surface area is 65～70cm3/ g, aperture is 3～4nm；Described bismuth sulfide is nano bar-shape knot
Structure, a length of 50～150nm, width is 5～10nm, is wrapped in around CNT；Described CNT plays pitman
Shape Bi2S3Function served as bridge, and at Bi2S3Scope outside surface has extended；Wherein, the specific surface of bismuth sulfide/CNT
Long-pending preferably 68.02cm3/ g, aperture is preferably 3.31nm.
Second technical problem to be solved by this invention is to provide the preparation of a kind of bismuth sulfide/carbon nano tube compound material
Method.
The preparation method of bismuth sulfide/carbon nano tube compound material, comprises the following steps:
A, it is 1:9～11 according to the mol ratio of bismuth Yu sulfur, takes five water bismuth nitrate and thioacetamides；According to product bismuth sulfide
0.11～0.12 times of quality, takes CNT, and CNT is carried out acidification；
B, by a step be acidified after CNT mix with thioacetamide, add water, ultrasonic 20～40min, obtain
Dispersion soln；The most ultrasonic 30min；
C, to add concentration in five water bismuth nitrate be the hydrochloric acid of 0.1mol/L～5mol/L, stirring, obtains transparent clarification molten
Liquid；
D, transparent clarification step c obtained is molten joins in the dispersion soln that step b obtains, stirring, obtains mixing molten
Liquid；
E, mixed solution Step d obtained react 10～15h at 110～130 DEG C, are cooled to room temperature, centrifugal, dry
Dry, grind, obtain bismuth sulfide/carbon nano tube compound material.
The preparation method of above-mentioned bismuth sulfide/carbon nano tube compound material, wherein five water bismuth nitrate are to be extracted by bismuthine
Arrive.
Further, the preparation method of above-mentioned bismuth sulfide/carbon nano tube compound material, wherein according to bismuth and sulfur in a step
Mol ratio be 1:10, take five water bismuth nitrate and thioacetamides.
Further, the preparation method of above-mentioned bismuth sulfide/carbon nano tube compound material, wherein in step e, mixed solution exists
12h is reacted at 120 DEG C.
The preparation method of above-mentioned bismuth sulfide/carbon nano tube compound material, wherein baking temperature is 60 DEG C, drying time 24h.
3rd technical problem to be solved by this invention be to provide a kind of bismuth sulfide/carbon nano tube compound material lithium from
Application in sub-battery.
The application in lithium ion battery of the above-mentioned bismuth sulfide/carbon nano tube compound material, wherein said lithium ion battery
Positive plate is to be prepared from by plus plate current-collecting body and anode sizing agent；Wherein, described anode sizing agent is by following weight ratio composition system
For forming: 80～the bismuth sulfide/carbon nano tube compound material of 95%, 2～the conductive agent of 10% and 3～the binding agent of 10%；Just
The slurry coating density in anode collection surface in pole is 50～200g/m2, preferably 100g/m2。
Further, the application in lithium ion battery of the above-mentioned bismuth sulfide/carbon nano tube compound material, wherein said positive pole
Slurry is preferably prepared from by following weight ratio composition: 80～the bismuth sulfide/carbon nano tube compound material of 90%, 5～10%
Conductive agent and 5～the binding agent of 10%.
Further, the application in lithium ion battery of the above-mentioned bismuth sulfide/carbon nano tube compound material, wherein said positive pole
Slurry is preferably prepared from by following weight ratio composition: the bismuth sulfide/carbon nano tube compound material of 90%, the conductive agent of 5% and
The binding agent of 5%.
The application in lithium ion battery of the above-mentioned bismuth sulfide/carbon nano tube compound material, wherein said plus plate current-collecting body is
Copper Foil, described conductive agent is at least one in nano-graphite, acetylene black, white carbon black；Described binding agent is Kynoar.
There is advantages that
1, CNT (CNT) can play the bar-shaped Bi of connection2S3Function served as bridge, and at Bi2S3Scope outside surface also has
Extended, it can be observed that Bi2S3Relatively it is uniformly adhered to decrease on flexible carbon pipe the generation of reunion.These are wrapped in CNT
Bi around2S3Nanorod length is 50～150nm, and width is 5～10nm；
2, CNT forms conductive network by being interconnected on electrode interior, for the transmission of electronics provide one the most logical
Road；
3、Bi2S3The specific surface area of/CNT is 68.02cm3/g, and aperture is 3.31nm, belongs to meso-hole structure, specific surface area and
Aperture is all higher than pure Bi2S3；Bigger specific surface area and aperture can reduce the volumetric expansion impact on electrode cycle life, carry
High reversible capacity, it is provided that good circulation energy；
4, the present invention lithium ion battery with bismuth sulfide/carbon nano tube compound material as positive electrode, has a following performance:
Relative to simple Bi2S3Electrode material, Bi2S3Button cell initial charge specific capacity prepared by/CNT combination electrode material is
861.3mAhg-1, first discharge specific capacity reaches 1173.9mAhg-1, first charge-discharge efficiency brings up to 73.4% from 69.5%,
After the visible CNT of utilization modifies, battery specific capacity and first charge-discharge efficiency are all improved；
5、Bi2S3/ CNT compares Bi2S3Maximum improvement is the raising of cycle performance, in electric current density 100mAg-1, electricity
0.01～2.5V circulation 50 times between nip；Bi2S3/ CNT specific capacity is by the 1173.9mAhg of first lap-1Fall sharply to the tenth circle
453.3mAhg-1, rate of descent is 61.4%；40 circle circulations subsequently are gradually stablized at the 50th circle, produces 246.3mAhg-1
Specific capacity；Relative to simple Bi2S3, Bi2S3/ CNT electrode material shows preferable cycle performance.
Accompanying drawing explanation
In Fig. 1, a, b, c are respectively Bi2S3, CNT and Bi2S3The XRD figure spectrum of/CNT；
Fig. 2 is Bi2S3The XRD partial enlargement collection of illustrative plates of/CNT；
Fig. 3 is Bi2S3The SEM figure of/CNT；
Fig. 4 is Bi2S3The TEM figure (embedded figure is SAED figure) of/CNT；
Fig. 5 is Bi2S3The isothermal adsorption desorption curve of/CNT；
Fig. 6 is Bi2S3The graph of pore diameter distribution of/CNT；
Fig. 7 is Bi2S3The charge and discharge platform test figure of/CNT；
Fig. 8 is Bi2S3/ CNT and Bi2S3Charge and discharge cycles test figure；
Fig. 9 is Bi2S3The cyclic voltammetry curve figure of/CNT；
Figure 10 is Bi2S3AC impedance figure before and after/CNT circulation；
Figure 11 is Bi2S3The multiplying power test figure of/CNT；
Figure 12 Bi2S3Charge and discharge platform test figure；
Figure 13 Bi2S3Charge and discharge cycles test figure；
Figure 14 Bi2S3Cyclic voltammetry curve figure.
Detailed description of the invention
Bismuth sulfide/carbon nano tube compound material of the present invention, this composite is meso-hole structure, wherein bismuth sulfide/carbon nanometer
The mass ratio of pipe is 1:0.11～0.12, and specific surface area is 65～70cm3/ g, aperture is 3～4nm；Described bismuth sulfide is nanometer
Club shaped structure, a length of 50～150nm, width is 5～10nm, is wrapped in around CNT；Described CNT plays
Connect bar-shaped Bi2S3Function served as bridge, and at Bi2S3Scope outside surface has extended, and meanwhile, CNT is connected with each other,
Form conductive network in electrode interior, provide an express passway for electric transmission；Wherein, the ratio table of bismuth sulfide/CNT
Area is preferably 68.02cm3/ g, aperture is preferably 3.31nm.
Bismuth sulfide/the carbon nano tube compound material of the present invention, uses the five water bismuth nitrate conducts being easier preparation storage
Reaction raw materials；It addition, use CNT mainly to have two effects as raw material: 1, CNT can play the bar-shaped Bi of connection2S3Bridge
Beam effect, and at Bi2S3Scope outside surface has extended, it can be observed that Bi2S3Relatively it is uniformly adhered to flexible carbon pipe
On decrease the generation of reunion；These are wrapped in the Bi around CNT2S3Nanorod length 50～150nm, width 5～
10nm；2, CNT forms conductive network by being interconnected on electrode interior, and the transmission for electronics provides an express passway.
The preparation method of bismuth sulfide/carbon nano tube compound material of the present invention, comprises the following steps:
A, it is 1:9～11 according to the mol ratio of bismuth Yu sulfur, takes five water bismuth nitrate and thioacetamides；According to product bismuth sulfide
0.11～0.12 times of quality, takes CNT, and CNT is carried out nitric acid acidification；
B, a step is acidified after CNT mix with thioacetamide, add deionized water, ultrasonic 20～
40min, the most ultrasonic 30min, obtain dispersion soln；Wherein, the CNT after the quality of deionized water is acidifying and sulfur generation
50～60 times of acetamide mixture gross mass；
C, to add concentration in five water bismuth nitrate be the hydrochloric acid of 0.1mol/L～5mol/L, stirring, obtains transparent clarification molten
Liquid；Wherein, the quality of hydrochloric acid is 15～20 times of five water bismuth nitrate quality；
D, transparent settled solution step c obtained join in the dispersion soln that step b obtains, stirring, are mixed
Solution；Stirring preferably employs magnetic agitation；
E, mixed solution Step d obtained hydro-thermal reaction 10～15h at 110～130 DEG C, be cooled to room temperature, add
Ionized water, is centrifuged with the centrifuge that rotating speed is 7000r/min, is repeated several times, and sample is carried out vacuum by isolated sample
It is dried, grinds, obtain bismuth sulfide/carbon nano tube compound material.
The preparation method of above-mentioned bismuth sulfide/carbon nano tube compound material, wherein five water bismuth nitrate are to be extracted by bismuthine
Arrive.
Further, the preparation method of above-mentioned bismuth sulfide/carbon nano tube compound material, wherein according to bismuth and sulfur in a step
Mol ratio be 1:10, take five water bismuth nitrate and thioacetamides.
Further, the preparation method of above-mentioned bismuth sulfide/carbon nano tube compound material, wherein in step e, mixed solution exists
12h is reacted at 120 DEG C.
The preparation method of above-mentioned bismuth sulfide/carbon nano tube compound material, wherein baking temperature is 60 DEG C, drying time 24h.
Bismuth sulfide/the carbon nano tube compound material of the present invention application in lithium ion battery, wherein said lithium ion battery
Including negative electrode casing, pad, high purity lithium sheet, electrolyte, barrier film, positive plate, anode cover, described barrier film is positioned at positive plate and high purity lithium
Between sheet, anode cover and negative electrode casing are wrapped in positive plate, barrier film, high purity lithium sheet periphery；Its positive plate be by plus plate current-collecting body and
Anode sizing agent is prepared from；Wherein, described anode sizing agent is to be prepared from by following weight ratio composition: 80～the sulfuration of 95%
Bismuth/carbon nano tube compound material, 2～the conductive agent of 10% and 3～the binding agent of 10%；Anode sizing agent is in anode collection surface
Coating density be 50～200g/m2, preferably 100g/m2。
Further, the application in lithium ion battery of the above-mentioned bismuth sulfide/carbon nano tube compound material, wherein said positive pole
Slurry is preferably prepared from by following weight ratio composition: 80～the bismuth sulfide/carbon nano tube compound material of 90%, 5～10%
Conductive agent and 5～the binding agent of 10%.
Further, the application in lithium ion battery of the above-mentioned bismuth sulfide/carbon nano tube compound material, wherein said positive pole
Slurry is preferably prepared from by following weight ratio composition: the bismuth sulfide/carbon nano tube compound material of 90%, the conductive agent of 5% and
The binding agent of 5%.
The application in lithium ion battery of the above-mentioned bismuth sulfide/carbon nano tube compound material, wherein said plus plate current-collecting body is
Copper Foil, described conductive agent is at least one in nano-graphite, acetylene black, white carbon black；Described binding agent is Kynoar.
Below in conjunction with embodiment, the detailed description of the invention of the present invention is further described, the most therefore the present invention is limited
System is among described scope of embodiments.
Embodiment 1
1, bismuth sulfide/carbon nano tube compound material is prepared
It is 1:10 according to the mol ratio of bismuth Yu sulfur, takes 0.485g five water bismuth nitrate and 0.751g thioacetamide, 30mg carbon
Nanotube, by CNT through pernitric acid acidification, mixes with thioacetamide after acidification, adds 50ml deionized water,
Ultrasonic 30min, obtains dispersion soln；Adding the hydrochloric acid of 5mL, 0.5mol/L in five water bismuth nitrate, stirring, until becoming transparent clear
Clear solution；Then transparent settled solution is added drop-wise in dispersion soln, magnetic agitation, obtains mixed solution；Mixed solution is put
Enter in reactor, at 120 DEG C, react 12h, be cooled to room temperature, obtain product, then by product and deionized water
Mixing to obtain mixture, be placed in a centrifuge centrifugal, be repeated several times, isolated sample, wherein, the quality of deionized water is reaction
200～300 times of product, centrifuge speed is 7000r/min；The sample of centrifugal gained is placed in vacuum drying oven drying,
Being transferred to after sample drying in agate mortar, be fully ground and obtain end product, wherein drying baker temperature is 60 DEG C, when being dried
Between be 24 hours, obtain bismuth sulfide/carbon nano tube compound material.
By above-mentioned gained bismuth sulfide/carbon nano tube compound material through XRD test, the collection of illustrative plates obtained as shown in Figure 1, Fig. 1
Showing a is simple Bi2S3The XRD figure of material, b is the XRD figure of CNT, and c is Bi2S3The XRD figure spectrum of/CNT composite；From figure
In (b) it can be seen that CNT is respectively belonging to the crystal face diffraction of 002 and 100 at 26.18 ° and 42.63 ° of diffraction maximums demonstrated
(JCPDS#41-1487) Bi formed after, adding a small amount of CNT2S3XRD figure spectrum and the single Bi of/CNT composite2S3Material
XRD figure spectrum consistent, remain the Bi of rhombic system2S3, with Bi2S3Base peak meets preferably, but the interpolation of CNT makes sample
Diffraction peak intensity somewhat weaken.Fig. 2 is Bi2S3The XRD partial enlargement collection of illustrative plates of/CNT, finds that sample occurs comparing at 26.18 °
Sharp-pointed diffraction maximum, belongs to the 002 crystal face diffraction of CNT, and further proof successfully prepares Bi2S3/ CNT composite；Will be multiple
Condensation material is tested through BET, and the specific surface area obtaining composite is 68.02cm3/g, and aperture is 3.31nm, and bismuth sulfide is in receiving
Rice club shaped structure, a length of 50～150nm, width is 5～10nm；Test through isothermal nitrogen adsorption desorption, can obtain from Fig. 5
Going out: this composite is mesoporous material, wherein CNT CNT can play the bar-shaped Bi of connection2S3Function served as bridge, and at Bi2S3
Scope outside surface has extended, Bi2S3Relatively it is uniformly adhered on flexible carbon pipe, decreases the generation of reunion；Simultaneously
CNT forms conductive network by being interconnected on electrode interior, for the transmission of electronics provide an express passway (see accompanying drawing 3,
4, shown in 6).
2, the preparation of the lithium ion battery with bismuth sulfide/carbon nano tube compound material as positive electrode
The present invention lithium ion battery with bismuth sulfide/carbon nano tube compound material as positive electrode, including negative electrode casing, pad
Sheet, high purity lithium sheet, electrolyte, barrier film, positive plate, anode cover, described barrier film between positive plate and high purity lithium sheet, anode cover
Being wrapped in positive plate, barrier film, high purity lithium sheet periphery with negative electrode casing, wherein positive plate is by plus plate current-collecting body and anode sizing agent manufacture
Become, described anode sizing agent by mass percentage by the bismuth sulfide/carbon nano tube compound material of 90%, the conductive agent white carbon black of 5% and
The binding agent Kynoar of 5% is mixed with and forms, and the anode sizing agent coating density in anode collection surface is 100g/
m2；Use test-type coating machine by slurry uniform application on conductive copper paillon foil, 60 DEG C of dry 12h in vacuum drying oven；With
Pole piece cutting machine goes out the circular pole piece of a diameter of 12mm.
The present embodiment is according to following steps assembled battery: glove box need to keep argon atmosphere, and moisture in case≤
200ppm；
One, the electrode slice prepared before utilizing is as working electrode, using high purity lithium sheet as to electrode, barrier film and electrolysis
Liquid, presses according to the order of negative electrode casing, pad, high purity lithium sheet, electrolyte, barrier film, electrolyte, positive plate and anode cover from bottom to up
Sequence assembles；
Two, utilize sealing machine at the good battery of glove box enclosed inside, wipe away excessive electrolyte be assembling complete；
Three, packaged battery need to stand 12h in glove box, and liquid to be electrolysed carries out electrochemistry after fully infiltrating pole piece
Can test.
Lithium ion battery with the bismuth sulfide/carbon nano tube compound material of the present invention as positive electrode, has a following performance:
Electric current density is 100mAg-1, voltage range is 0.01～2.5V, relative to simple Bi2S3Electrode material (as shown in Figure 8),
Bi2S3Button cell initial charge specific capacity prepared by/CNT combination electrode material is 861.3mAhg-1, first discharge specific capacity
Reach 1173.9mAhg-1, first charge-discharge efficiency is 73.4%, it is seen that after utilizing CNT to modify, battery specific capacity and first
Efficiency for charge-discharge is all improved；Can be seen that charging and discharging capacity all has declining in various degree from second time charging and discharging curve
Subtract, in electric current density 100mAg-1, voltage range 0.01～2.5V circulates 50 times.Bi2S3/ CNT specific capacity is by first lap
1173.9mAhg-1Fall sharply to the 453.3mAhg of the tenth circle-1, rate of descent is 61.4%；40 circles subsequently are the most steady in circulating
It is scheduled on the 50th circle, produces 246.3mAhg-1Specific capacity (its charge and discharge platform test figure, cyclic voltammetry curve figure, circulate before and after
AC impedance figure and multiplying power test figure respectively as shown in Fig. 7,9,10,11).
Comparative example 1
This comparative example is that bismuth sulfide material passes through five water bismuth nitrate (Bi (NO3)3·5H2And thioacetamide O)
(CH3CSNH2) use water heat transfer as predecessor.Prepare by following experimental procedure:
One, it is 1:10 according to the mol ratio of bismuth Yu sulfur, takes 0.485g five water bismuth nitrate and 0.751g thioacetamide；
Two, by CH3CSNH2Being dissolved in 50mL deionized water, ultrasonic disperse 30min, to uniformly, obtains solution A；
Three, another by Bi (NO3)3·5H2O be dissolved in 5mL, 0, in the hydrochloric acid of 5mol/L, be sufficiently stirred for obtaining transparent clarification molten
Liquid B；
Four, two kinds of solution mixing of A, B are placed in the hydrothermal reaction kettle of 100mL, react 5 hours at a temperature of 100 DEG C；
Five, will cooling after product deionized water and dehydrated alcohol cyclic washing for several times, with 7000 turns/min's
Speed is centrifuged；
Six, the sample after being centrifuged is 60 DEG C of drying 24h in vacuum drying oven；
Seven, transfer to, in agate mortar, be fully ground and obtain end product after sample drying.
Positive plate is prepared according to following steps:
1), bismuth sulfide, conductive black and Kynoar (PVDF) are weighed according to mass ratio 90:5:5 respectively；
2), load weighted PVDF joined in beaker and in beaker, add appropriate N-Methyl pyrrolidone (NMP)
Solution, continuing magnetic force stirring 24h obtains uniform solution；
3), in this solution, add load weighted bismuth sulfide and conductive black, continue magnetic agitation 12h and starched uniformly
Material；
4), use test-type coating machine by slurry uniform application on conductive copper paillon foil, do for 60 DEG C in vacuum drying oven
Dry 12h；
5) the circular pole piece of a diameter of 12mm, is gone out with pole piece cutting machine.
According to following steps assembled battery in this experimental program:
Glove box need to keep argon atmosphere, moisture≤200ppm in case；
, utilize before the electrode slice for preparing as working electrode, using high purity lithium sheet as to electrode, barrier film and electrolysis
Liquid, presses according to the order of negative electrode casing, pad, high purity lithium sheet, electrolyte, barrier film, electrolyte, positive plate and anode cover from bottom to up
Sequence assembles；
, utilize sealing machine at the good battery of glove box enclosed inside, wipe away excessive electrolyte be assembling complete；
, packaged battery need to stand 12h in glove box, liquid to be electrolysed carries out electrochemistry after fully infiltrating pole piece
Can test: (its charge and discharge platform test figure, charge and discharge cycles test figure and cyclic voltammetry curve figure are shown in Figure 12,13 and 14 respectively
Shown in), at 100mAg-1Under electric current density, specific capacity is by initial 580.2mAhg-1Reduce to 389.7mAhg-1, subsequently
200mAg-1、500mAg-1Show relatively stable during test, respectively reached 127.4mAhg-1And 63.8mAhg-1, passing through
1000mAg-1100mAg is returned to after heavy-current discharge-1Low discharging current, specific capacity is by 33.1mAhg-1Again rise to
187.6mAhg-1。
Claims (10)
1. bismuth sulfide/carbon nano tube compound material, it is characterised in that: described composite is meso-hole structure, wherein bismuth sulfide/carbon
The mass ratio of nanotube is 1:0.11～0.12, and specific surface area is 65～70cm3/ g, aperture is 3～4nm；Described bismuth sulfide is
Nano bar-shape structure, a length of 50～150nm, width is 5～10nm, is wrapped in around CNT；Described CNT
Play the bar-shaped Bi of connection2S3Function served as bridge, and at Bi2S3Scope outside surface has extended；Wherein, bismuth sulfide/carbon nanometer
The specific surface area of pipe is preferably 68.02cm3/ g, aperture is preferably 3.31nm.
2. the preparation method of bismuth sulfide/carbon nano tube compound material described in claim 1, it is characterised in that comprise the following steps:
A, it is 1:9～11 according to the mol ratio of bismuth Yu sulfur, takes five water bismuth nitrate and thioacetamides；According to product bismuth sulfide quality
0.11～0.12 times, take CNT, and CNT carried out acidification；
B, by a step be acidified after CNT mix with thioacetamide, add water, ultrasonic 20～40min, disperseed
Solution；The most ultrasonic 30min；
C, to add concentration in five water bismuth nitrate be the hydrochloric acid of 0.1mol/L～5mol/L, stirring, obtains transparent settled solution；
D, transparent settled solution step c obtained join in the dispersion soln that step b obtains, stirring, obtain mixed solution；
E, mixed solution Step d obtained react 10～15h at 110～130 DEG C, are cooled to room temperature, centrifugal, are dried, grind
Mill, obtains bismuth sulfide/carbon nano tube compound material.
The preparation method of bismuth sulfide/carbon nano tube compound material the most according to claim 2, it is characterised in that: five liquid glauber salt acid
Bismuth is to be extracted by bismuthine to obtain.
4. according to the preparation method of bismuth sulfide/carbon nano tube compound material described in Claims 2 or 3, it is characterised in that: a step
In be 1:10 according to the mol ratio of bismuth Yu sulfur, take five water bismuth nitrate and thioacetamides.
The preparation method of bismuth sulfide/carbon nano tube compound material the most according to claim 2, it is characterised in that: mixed in step e
Close solution at 120 DEG C, react 12h.
The preparation method of bismuth sulfide/carbon nano tube compound material the most according to claim 2, it is characterised in that: baking temperature
Be 60 DEG C, drying time 24h.
7. bismuth sulfide/carbon nano tube compound material application in lithium ion battery described in claim 1, it is characterised in that: institute
The positive plate stating lithium ion battery is to be prepared from by plus plate current-collecting body and anode sizing agent；Wherein, described anode sizing agent be by with
Lower weight ratio composition is prepared from: 80～the bismuth sulfide/carbon nano tube compound material of 95%, 2～the conductive agent of 10% and 3～
The binding agent of 10%；The anode sizing agent coating density in anode collection surface is 50～200g/m2, preferably 100g/m2。
Apply the most according to claim 7, it is characterised in that: described anode sizing agent is by the preparation of following weight ratio composition
Become: 80～the bismuth sulfide/carbon nano tube compound material of 90%, 5～the conductive agent of 10% and 5～the binding agent of 10%.
Apply the most according to claim 8, it is characterised in that: described anode sizing agent is by the preparation of following weight ratio composition
Become: the bismuth sulfide/carbon nano tube compound material of 90%, the conductive agent of 5% and the binding agent of 5%.
10. according to described in any one of claim 7～9 apply, it is characterised in that: described plus plate current-collecting body is Copper Foil, described in lead
Electricity agent is at least one in nano-graphite, acetylene black, white carbon black；Described binding agent is Kynoar.
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| CN107146915A (en) * | 2017-04-10 | 2017-09-08 | 中山大学 | A kind of preparation method of porous bismuth carbon composite |
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| CN110217819B (en) * | 2019-07-01 | 2022-02-08 | 山西医科大学 | One-step synthesis method of spherical hollow mesoporous bismuth sulfide/silicon dioxide nano material |
| CN110534722A (en) * | 2019-09-16 | 2019-12-03 | 福州大学 | A kind of preparation method of novel multi-cavity clad structure bismuth sulfide/cobalt sulfide combination electrode material |
| CN110534722B (en) * | 2019-09-16 | 2022-04-19 | 福州大学 | Preparation method of bismuth sulfide/cobalt sulfide composite electrode material with multi-cavity coating structure |
| CN113677052A (en) * | 2021-09-08 | 2021-11-19 | 湖北中烟工业有限责任公司 | Electric heating material based on strong coupling of bismuth sulfide and carbon nano tube and preparation method thereof |
| CN113677052B (en) * | 2021-09-08 | 2024-04-26 | 湖北中烟工业有限责任公司 | Electric heating material based on strong coupling of bismuth sulfide and carbon nano tube and preparation method thereof |
| CN114695881A (en) * | 2022-04-22 | 2022-07-01 | 河北科技大学 | Bismuth sulfide negative electrode material and preparation method and application thereof |
| CN114695881B (en) * | 2022-04-22 | 2024-04-12 | 河北科技大学 | Bismuth sulfide anode material and preparation method and application thereof |
| CN115896857A (en) * | 2022-12-30 | 2023-04-04 | 重庆大学 | Bismuth sulfide-carbon nano material and preparation method and application thereof |
| CN115896857B (en) * | 2022-12-30 | 2023-12-15 | 重庆大学 | Bismuth sulfide-carbon nanomaterial and preparation method and application thereof |
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