CN109285992A - A kind of molybdenum sulfide flexible electrode material and its preparation method and application - Google Patents
A kind of molybdenum sulfide flexible electrode material and its preparation method and application Download PDFInfo
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- CN109285992A CN109285992A CN201710590354.XA CN201710590354A CN109285992A CN 109285992 A CN109285992 A CN 109285992A CN 201710590354 A CN201710590354 A CN 201710590354A CN 109285992 A CN109285992 A CN 109285992A
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- H—ELECTRICITY
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- 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
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- H—ELECTRICITY
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- 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
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- 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
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
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Abstract
The present invention relates to a kind of molybdenum sulfide flexible electrode materials and its preparation method and application, the method are as follows: in cotton class carbon source surface splash elemental metals, then it is mixed with molybdenum source, ammonium fluoride and urea, hydro-thermal reaction is carried out, is separated by solid-liquid separation after the reaction was completed, obtains persursor material, persursor material and sulphur source are mixed, secondary hydro-thermal reaction is carried out, is separated by solid-liquid separation after the reaction was completed, molybdenum sulfide flexible electrode material is obtained after Overheating Treatment.The present invention directly uses discarded cotton material or most of material for being cotton as carbon source and template, economic and environment-friendly；The generation temperature of molybdenum sulfide is reduced using two step vulcanizations using metal as catalyst, keeps the flexibility and integrality of cotton material；When the molybdenum sulfide flexible electrode material being prepared is as lithium ion battery negative material, there is excellent chemical property, first charge-discharge reversible specific capacity has broad application prospects up to 800-1400mAh/g.
Description
Technical field
The present invention relates to field of nano material preparation, and in particular to a kind of molybdenum sulfide flexible electrode material and preparation method thereof
And application.
Background technique
The rise of flexible wearable electronic equipment has pushed the fast development of flexible energy storage technology.As flexible energy storage
The part of core, the preparation and assembling of flexible electrode directly determine the performance level of flexible energy storage device the most in device.Cotton
Class material has good flexibility, frivolous, cheap, environmental-friendly, can be carbonized, have good through high-temperature heat treatment
Electric conductivity, the substrate that can be used as material use.
Molybdenum sulfide (MoS2) there is class graphene two-dimensional layered structure, it is very ideal lithium ion battery negative material.
But in cyclic process, it is molybdenum and lithium sulfide as molybdenum disulfide reacts completely, biggish volume change can be caused, reduced
Its cyclical stability.Further, since molybdenum disulfide native electronic conductance is poor, so that its high rate performance is not good enough.
Cotton-like material is a kind of biomaterial being widely present in nature, can be carbonized to obtain at high temperature and lead with height
Electrical carbon material, while retaining its primary morphology, good biological template is provided to prepare combination electrode material.Use cotton
Class material can significantly alleviate the recycling problem of cotton clothes etc. as carbon source, while mention to prepare combination electrode material
Cheap carbon source has been supplied, it is environmentally protective, meet the demand of low carbon development.It, can using cotton-like material as molybdenum sulfide substrate
So that molybdenum sulfide is directly grown in cotton fiber surface, improves material electronics conductance, while obtaining the flexibility with certain mechanical strength
Electrode material.But the synthesis temperature of molybdenum sulfide is higher, under high temperature and pressure thermal and hydric environment, is easy to cause the broken of cotton, it is difficult to
Keep pattern.
Summary of the invention
In view of problems of the prior art, the present invention provides a kind of molybdenum sulfide flexible electrode material and its preparation sides
Method and application, using cotton-like material as carbon source, elemental metals are as catalyst, using two step vulcanizations, have been prepared with excellent
The molybdenum sulfide flexible electrode material of different chemical property.
To achieve this purpose, the present invention adopts the following technical scheme:
In a first aspect, the present invention provides a kind of preparation method of molybdenum sulfide flexible electrode material, the method includes with
Lower step:
(1) in cotton class carbon source surface splash elemental metals；
(2) material that step (1) obtains is mixed with molybdenum source, ammonium fluoride and urea, carries out hydro-thermal reaction, after the reaction was completed
It is separated by solid-liquid separation, obtains persursor material；
(3) persursor material and the sulphur source mixing obtained step (2), carries out secondary hydro-thermal reaction, solid after the reaction was completed
Liquid separation；
(4) material that step (3) obtains is heat-treated, obtains molybdenum sulfide flexible electrode material.
Cotton-like material is mostly doughnut structure, thermally treated to be carbonized as carbon micron tube, while itself having capillary effect
It answers, using capillary effect and bond to surface, molybdenum sulfide can be made to be directly grown in carbon micron tube surface.Obtained molybdenum sulfide
Flexible electrode material has doughnut pilotaxitic texture, is conducive to the abundant infiltration of electrolyte, can shorten lithium ion and electronics
Transmission path increases with the contact area of electrolyte, provides more reactivity positions, while can fender to a certain extent
The volume change in cyclic process is expected, so as to improve the high rate performance and cyclical stability of material.
Present invention proposition is adopted in one layer of metal of cotton-like material surface splash using the high catalytic activity of metal simultaneously first
The mode vulcanized with two steps completes the exchange process of sulphion and oxonium ion, obtains molybdenum sulfide flexible electrode material.Elemental metals
Catalysis characteristics with higher can reduce the synthesis temperature of molybdenum sulfide using its catalysis characteristics, keep the flexible of cotton-like material
Property, to obtain molybdenum sulfide flexible electrode material.
According to the present invention, step (1) the cotton class carbon source is cotton material, preferably clothes, towel, cotton or non-dust cloth
In any one or at least two combination；Such as it can be any one in clothes, towel, cotton or non-dust cloth, allusion quotation
Type but non-limiting group is combined into clothes and towel；Clothes and cotton；Towel and cotton；Cotton and non-dust cloth；Clothes, towel and
Cotton；Towel, cotton and non-dust cloth etc., as space is limited and for concise consideration, the present invention no longer exclusive list.
According to the present invention, step (1) elemental metals are any one in gold, silver, copper, nickel or iron.
According to the present invention, step (1) elemental metals and the mass ratio of cotton class carbon source are (0.001-10): 1, preferably
(0.01-0.5):1；Such as it can be 1:1000,1:500,1:100,1:50,1:10,1:5,1:2,1:1,2:1,5:1 or 10:
Specific point value between 1 and above-mentioned numerical value, as space is limited and for concise consideration, the present invention no longer exclusive list.
Under normal conditions, in step (1) in cotton class carbon source one layer of elemental metals of surface splash, can also splash multilayer,
Particular determination is not done to this.
According to the present invention, step (2) molybdenum source is ammonium molybdate, sodium molybdate, ammonium thiomolybdate, molybdenum chloride or acetylacetone,2,4-pentanedione
In molybdenum any one or at least two combination；Such as it can be ammonium molybdate, sodium molybdate, ammonium thiomolybdate, molybdenum chloride or second
Any one in acyl acetone molybdenum, typical but non-limiting combination are as follows: ammonium molybdate and sodium molybdate；Ammonium thiomolybdate and chlorination
Molybdenum；Ammonium molybdate and molybdenum chloride；Molybdenum chloride and acetyl acetone；Ammonium molybdate and ammonium thiomolybdate；Ammonium molybdate, sodium molybdate and molybdenum dithiophosphate
Sour ammonium；Ammonium thiomolybdate, molybdenum chloride and acetyl acetone etc., as space is limited and for concise consideration, the present invention is no longer exhaustive
It enumerates.
According to the present invention, the mass ratio of step (2) molybdenum source and step (1) described cotton class carbon source is (0.1-40): 1,
Preferably (0.5-4): 1；Such as can be 1:10,1:5,1:2,1:1,2:1,5:1,10:1,15:1,20:1,25:1,30:1,
Specific point value between 35:1 or 40:1 and above-mentioned numerical value, as space is limited and for concise consideration, the present invention is no longer exhaustive
It enumerates.
According to the present invention, step (2) molybdenum source and the molar ratio of ammonium fluoride are 1:(0.05-20), preferably 1:(0.1-
10)；Such as it can be 20:1,15:1,10:1,5:1,2:1,1:1,1:2,1:5,1:10,1:15 or 1:20 and above-mentioned numerical value
Between specific point value, as space is limited and for concise consideration, the present invention no longer exclusive list.
According to the present invention, step (2) molybdenum source and the molar ratio of urea are 1:(0.1-20), preferably 1:(0.5-
10)；Such as it can be specific between 10:1,5:1,2:1,1:1,1:2,1:5,1:10,1:15 or 1:20 and above-mentioned numerical value
Point value, as space is limited and for concise consideration, the present invention no longer exclusive list.
According to the present invention, the temperature of step (2) described hydro-thermal reaction is 90-200 DEG C, preferably 100-150 DEG C；Such as it can
To be 90 DEG C, 100 DEG C, 110 DEG C, 120 DEG C, 130 DEG C, 140 DEG C, 150 DEG C, 160 DEG C, 170 DEG C, 180 DEG C, 190 DEG C or 200 DEG C,
And the specific point value between above-mentioned numerical value, as space is limited and for concise consideration, the present invention no longer exclusive list.
Preferably, the pressure of step (2) described hydro-thermal reaction is 2-30MPa, preferably 5-20MPa；Such as it can be
2MPa, 5MPa, 8MPa, 10MPa, 12MPa, 15MPa, 18MPa, 20MPa, 23MPa, 25MPa, 28MPa or 30MPa, Yi Jishang
The specific point value between numerical value is stated, as space is limited and for concise consideration, the present invention no longer exclusive list.
Preferably, the time of step (2) described hydro-thermal reaction is 2-72h, preferably 15-30h；Such as can be 2h, 5h,
Between 10h, 15h, 18h, 20h, 25h, 28h, 30h, 35h, 40h, 45h, 50h, 55h, 60h, 65h or 72h and above-mentioned numerical value
Specific point value, as space is limited and for concise consideration, the present invention no longer exclusive list.
According to the present invention, step (3) sulphur source be vulcanized sodium, sodium thiosulfate or thiocarbamide in any one or at least
Two kinds of combination；Such as it can be any one in vulcanized sodium, sodium thiosulfate or thiocarbamide, typical but non-limiting combination
Are as follows: vulcanized sodium and sodium thiosulfate；Vulcanized sodium and thiocarbamide；Sodium thiosulfate and thiocarbamide；Vulcanized sodium, sodium thiosulfate and thiocarbamide.
According to the present invention, the molar ratio of step (3) sulphur source and step (2) described molybdenum source is 1:(0.5-10), preferably
For 1:(1-5)；Such as it can be 2:1,1:1,1:2,1:3,1:4,1:5,1:6,1:7,1:8,1:9 or 1:10 and above-mentioned number
Specific point value between value, as space is limited and for concise consideration, the present invention no longer exclusive list.
According to the present invention, the temperature of step (3) the secondary hydro-thermal reaction is 80-150 DEG C, preferably 90-120 DEG C；Example
Such as can be 80 DEG C, 85 DEG C, 90 DEG C, 95 DEG C, 100 DEG C, 105 DEG C, 110 DEG C, 115 DEG C, 120 DEG C, 125 DEG C, 130 DEG C, 135 DEG C,
Specific point value between 140 DEG C, 145 DEG C or 150 DEG C and above-mentioned numerical value, as space is limited and for concise consideration, the present invention
No longer exclusive list.
According to the present invention, the pressure of step (3) the secondary hydro-thermal reaction is 2-30MPa, preferably 5-20MPa；Such as
It can be 2MPa, 5MPa, 8MPa, 10MPa, 12MPa, 15MPa, 18MPa, 20MPa, 23MPa, 25MPa, 28MPa or 30MPa,
And the specific point value between above-mentioned numerical value, as space is limited and for concise consideration, the present invention no longer exclusive list.
According to the present invention, the time of step (3) the secondary hydro-thermal reaction is 2-20h, preferably 5-12h；Such as it can be with
It is the specific point value between 2h, 5h, 8h, 10h, 12h, 15h, 18h or 20h and above-mentioned numerical value, as space is limited and for simplicity
The considerations of, the present invention no longer exclusive list.
According to the present invention, the temperature of step (4) described heat treatment is 500-1000 DEG C, preferably 700-900 DEG C；Such as it can
To be 500 DEG C, 550 DEG C, 600 DEG C, 650 DEG C, 700 DEG C, 750 DEG C, 800 DEG C, 850 DEG C, 900 DEG C, 950 DEG C or 1000 DEG C, and
Specific point value between above-mentioned numerical value, as space is limited and for concise consideration, the present invention no longer exclusive list.
According to the present invention, the time of step (4) described heat treatment is 0.5-10h, preferably 1-4h；Such as it can be
Specific point value between 0.5h, 1h, 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h or 10h and above-mentioned numerical value as space is limited and goes out
In concise consideration, the present invention no longer exclusive list.
Separation of solid and liquid of the present invention selects means well known in the art to carry out, such as can be filtering, suction filtration, centrifugation
Deng, but it is non-be only limitted to this, should be advisable in actual mechanical process in order to operate.
Second aspect, the present invention provide a kind of molybdenum sulfide flexible electrode material that method as described in relation to the first aspect is prepared
Material.
The third aspect, the present invention provides a kind of application of molybdenum sulfide flexible electrode material as described in second aspect, described
Molybdenum sulfide flexible electrode material is used as lithium ion battery negative material, anode material of lithium-ion battery, electrode of super capacitor material
Material or liberation of hydrogen material.
Compared with prior art, the present invention is at least had the advantages that
(1) preparation process directly uses discarded cotton material or most of material for being cotton as carbon source and template,
It is environmentally protective, while production cost is greatly reduced.
(2) using metal as catalyst, using two step vulcanizations, to reduce the generation temperature of molybdenum sulfide, cotton is kept
The flexibility and integrality of material.
(3) when the molybdenum sulfide flexible electrode material being prepared is as lithium ion battery negative material, there is excellent electricity
Chemical property, first charge-discharge reversible specific capacity be 800-1400mAh/g, can also be used as anode material of lithium-ion battery or
Electrode material for super capacitor is applied in energy storage field.
(4) preparation process is easy to operate, flexible, and reaction condition is mild, is suitable for industrialized production, has wide application
Prospect.
Detailed description of the invention
Fig. 1 is molybdenum sulfide flexible electrode material the filling as lithium ion battery negative material that the embodiment of the present invention 1 obtains
Discharge curve, in figure, abscissa is cycle-index, and ordinate is specific capacity.
The present invention is described in more detail below.But following examples is only simple example of the invention, not generation
Table or limitation the scope of the present invention, protection scope of the present invention are subject to claims.
Specific embodiment
To further illustrate the technical scheme of the present invention below with reference to the accompanying drawings and specific embodiments.
In order to better illustrate the present invention, it is easy to understand technical solution of the present invention, of the invention is typical but non-limiting
Embodiment is as follows:
Embodiment 1
(1) in one layer of gold of cotton surface splash, the golden mass ratio with cotton is 1:5；
(2) material that step (1) obtains is mixed with ammonium molybdate, ammonium fluoride and urea, wherein the matter of cotton and ammonium molybdate
For amount than being 1:1, the molar ratio of ammonium molybdate, ammonium fluoride and urea is 1:2:4, and mixture is transferred in closed reactor, is being dried
Hydro-thermal for 24 hours, is separated by solid-liquid separation after the reaction was completed at 150 DEG C in case, and cleaning obtains presoma；
(3) presoma and the vulcanized sodium mixing obtained step (2), wherein the molar ratio of vulcanized sodium and ammonium molybdate is 1:4,
It is again transferred in closed reactor, hydro-thermal 10h at 100 DEG C, is separated by solid-liquid separation after the reaction was completed in baking oven, cleaning；
(4) material that step (3) obtains is heat-treated 3h at 750 DEG C, obtains molybdenum sulfide flexible electrode material.
The molybdenum sulfide flexible electrode material that the present embodiment is obtained carries out electrification directly as lithium ion battery negative material
Performance test is learned, CR2032 type button cell is prepared.It is surveyed under 0.01-3.0V voltage window, 100mA/g current density
Examination.
As a result as shown in Figure 1, the obtained molybdenum sulfide flexible electrode material of the present embodiment is as negative electrode of lithium ion battery material
When material, higher reversible specific capacity is shown.Circulation specific discharge capacity is 1450mAh/g for the first time, and charge specific capacity is
1100mAh/g.Second of circulation specific discharge capacity is 1100mAh/g, charge specific capacity 1050mAh/g.
Embodiment 2
(1) in one layer of silver of non-dust cloth surface splash, the silver-colored mass ratio with non-dust cloth is 1:8；
(2) material that step (1) obtains is mixed with ammonium thiomolybdate, ammonium fluoride and urea, wherein ammonium thiomolybdate with
The mass ratio of non-dust cloth is 4:1, and the molar ratio of ammonium thiomolybdate, ammonium fluoride and urea is 1:3:5, mixture is transferred to closed
In reaction kettle, hydro-thermal 5h at 200 DEG C, is separated by solid-liquid separation after the reaction was completed in baking oven, and cleaning obtains presoma；
(3) presoma and the sodium thiosulfate mixing that obtain step (2), wherein sodium thiosulfate and ammonium thiomolybdate
Molar ratio is 1:2, is again transferred in closed reactor, and hydro-thermal 8h at 120 DEG C, is separated by solid-liquid separation after the reaction was completed in baking oven,
Cleaning；
(4) material that step (3) obtains is heat-treated 2.5h at 800 DEG C, obtains molybdenum sulfide flexible electrode material.
The molybdenum sulfide flexible electrode material that the present embodiment is obtained carries out electrification directly as lithium ion battery negative material
Performance test is learned, test method is the same as embodiment 1.
The results show that the molybdenum sulfide flexible electrode material that the present embodiment obtains is when as lithium ion battery negative material,
Show higher reversible specific capacity.Circulation specific discharge capacity is 1050mAh/g, charge specific capacity 1000mAh/g for the first time.The
Secondary cycle specific discharge capacity is 970mAh/g, charge specific capacity 950mAh/g.
Embodiment 3
(1) in one layer of copper of cotton surface splash, the mass ratio of copper and non-dust cloth is 1:10；
(2) material that step (1) obtains is mixed with sodium molybdate, ammonium fluoride and urea, wherein sodium molybdate and non-dust cloth
Mass ratio is 3:1, and the molar ratio of sodium molybdate, ammonium fluoride and urea is 1:10:10, and mixture is transferred in closed reactor,
Hydro-thermal 20h at 120 DEG C, is separated by solid-liquid separation after the reaction was completed in baking oven, and cleaning obtains presoma；
(3) presoma and the vulcanized sodium mixing obtained step (2), wherein the molar ratio of vulcanized sodium and sodium molybdate is 1:3,
It is again transferred in closed reactor, hydro-thermal 12h at 90 DEG C, is separated by solid-liquid separation after the reaction was completed in baking oven, cleaning；
(4) material that step (3) obtains is heat-treated 1h at 1000 DEG C, obtains molybdenum sulfide flexible electrode material.
The molybdenum sulfide flexible electrode material that the present embodiment is obtained carries out electrification directly as lithium ion battery negative material
Performance test is learned, test method is the same as embodiment 1.
The results show that the molybdenum sulfide flexible electrode material that the present embodiment obtains is when as lithium ion battery negative material,
Show higher reversible specific capacity.Circulation specific discharge capacity is 1480mAh/g, charge specific capacity 1360mAh/g for the first time.The
Secondary cycle specific discharge capacity is 1320mAh/g, charge specific capacity 1300mAh/g.
Embodiment 4
(1) in one layer of nickel of garment surface splash, the mass ratio of nickel and clothes is 1:20；
(2) material that step (1) obtains is mixed with molybdenum chloride, ammonium fluoride and urea, wherein the matter of molybdenum chloride and clothes
For amount than being 2:1, the molar ratio of molybdenum chloride, ammonium fluoride and urea is 1:1:5, and mixture is transferred in closed reactor, is being dried
Hydro-thermal 18h at 140 DEG C, is separated by solid-liquid separation after the reaction was completed in case, and cleaning obtains presoma；
(3) presoma and the thiocarbamide mixing obtained step (2), wherein the molar ratio of thiocarbamide and molybdenum chloride is 1:5, again
It is transferred in closed reactor, hydro-thermal 20h at 80 DEG C, is separated by solid-liquid separation after the reaction was completed in baking oven, cleaning；
(4) material that step (3) obtains is heat-treated 1.5h at 900 DEG C, obtains molybdenum sulfide flexible electrode material.
The molybdenum sulfide flexible electrode material that the present embodiment is obtained carries out electrification directly as lithium ion battery negative material
Performance test is learned, test method is the same as embodiment 1.
The results show that the molybdenum sulfide flexible electrode material that the present embodiment obtains is when as lithium ion battery negative material,
Show higher reversible specific capacity.Circulation specific discharge capacity is 960mAh/g, charge specific capacity 900mAh/g for the first time.Second
Secondary circulation specific discharge capacity is 850mAh/g, charge specific capacity 840mAh/g.
Embodiment 5
(1) in one layer of iron of cotton surface splash, the mass ratio of iron and cotton is 1:15；
(2) material that step (1) obtains is mixed with ammonium molybdate, ammonium fluoride and urea, wherein the matter of ammonium molybdate and cotton
For amount than being 1:1, the molar ratio of ammonium molybdate, ammonium fluoride and urea is 1:3:6, and mixture is transferred in closed reactor, is being dried
Hydro-thermal 15h at 150 DEG C, is separated by solid-liquid separation after the reaction was completed in case, and cleaning obtains presoma；
(3) presoma and the thiocarbamide mixing obtained step (2), wherein the molar ratio of thiocarbamide and ammonium molybdate is 1:1, again
It is transferred in closed reactor, hydro-thermal 10h at 100 DEG C, is separated by solid-liquid separation after the reaction was completed in baking oven, cleaning；
(4) material that step (3) obtains is heat-treated 2.5h at 850 DEG C, obtains molybdenum sulfide flexible electrode material.
The molybdenum sulfide flexible electrode material that the present embodiment is obtained carries out electrification directly as lithium ion battery negative material
Performance test is learned, test method is the same as embodiment 1.
The results show that the molybdenum sulfide flexible electrode material that the present embodiment obtains is when as lithium ion battery negative material,
Show higher reversible specific capacity.Circulation specific discharge capacity is 1100mAh/g, charge specific capacity 1020mAh/g for the first time.The
Secondary cycle specific discharge capacity is 1050mAh/g, charge specific capacity 1000mAh/g.
Comparative example 1
Compared with Example 1, in addition to removing step 1, other steps and condition and embodiment 1 are all the same, i.e., directly by cotton
Cloth and ammonium molybdate, ammonium fluoride and urea mixing, the operation without splash gold.
The molybdenum sulfide electrode material that this comparative example is obtained carries out electrochemistry directly as lithium ion battery negative material
It can test, test method is the same as embodiment 1.
The results show that the molybdenum sulfide electrode material that this comparative example obtains is when as lithium ion battery negative material.For the first time
Circulation specific discharge capacity is 850mAh/g, charge specific capacity 790mAh/g.Second of circulation specific discharge capacity is 700mAh/g,
Charge specific capacity is 690mAh/g.
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above
Detail within the scope of the technical concept of the present invention can be with various simple variants of the technical solution of the present invention are made, this
A little simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance
In the case where shield, can be combined in any appropriate way, in order to avoid unnecessary repetition, the present invention to it is various can
No further explanation will be given for the combination of energy.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should also be regarded as the disclosure of the present invention.
Claims (10)
1. a kind of preparation method of molybdenum sulfide flexible electrode material, which is characterized in that the described method comprises the following steps:
(1) in cotton class carbon source surface splash elemental metals；
(2) material that step (1) obtains is mixed with molybdenum source, ammonium fluoride and urea, carries out hydro-thermal reaction, after the reaction was completed solid-liquid
Separation, obtains persursor material；
(3) persursor material and the sulphur source mixing obtained step (2), carries out secondary hydro-thermal reaction, after the reaction was completed solid-liquid point
From；
(4) material that step (3) obtains is heat-treated, obtains molybdenum sulfide flexible electrode material.
2. the method as described in claim 1, which is characterized in that step (1) the cotton class carbon source is cotton material, preferably clothing
In clothes, towel, cotton or non-dust cloth any one or at least two combination.
3. method according to claim 1 or 2, which is characterized in that step (1) elemental metals be gold, silver, copper, nickel or
Any one in iron；
Preferably, step (1) elemental metals and the mass ratio of cotton class carbon source are (0.001-10): 1, preferably (0.01-
0.5):1。
4. the method according to claim 1, which is characterized in that step (2) molybdenum source is ammonium molybdate, molybdic acid
In sodium, ammonium thiomolybdate, molybdenum chloride or acetyl acetone any one or at least two combination；
Preferably, the mass ratio of step (2) molybdenum source and step (1) described cotton class carbon source is (0.1-40): 1, preferably
(0.5-4):1；
Preferably, step (2) molybdenum source and the molar ratio of ammonium fluoride are 1:(0.05-20), preferably 1:(0.1-10)；
Preferably, step (2) molybdenum source and the molar ratio of urea are 1:(0.1-20), preferably 1:(0.5-10).
5. method according to any of claims 1-4, which is characterized in that the temperature of step (2) described hydro-thermal reaction is 90-
200 DEG C, preferably 100-150 DEG C；
Preferably, the pressure of step (2) described hydro-thermal reaction is 2-30MPa, preferably 5-20MPa；
Preferably, the time of step (2) described hydro-thermal reaction is 2-72h, preferably 15-30h.
6. the method according to claim 1 to 5, which is characterized in that step (3) sulphur source is vulcanized sodium, thio sulphur
In sour sodium or thiocarbamide any one or at least two combination；
Preferably, the molar ratio of step (3) sulphur source and step (2) described molybdenum source is 1:(0.5-10), preferably 1:(1-
5)。
7. as the method according to claim 1 to 6, which is characterized in that the temperature of step (3) the secondary hydro-thermal reaction
It is 80-150 DEG C, preferably 90-120 DEG C；
Preferably, the pressure of step (3) the secondary hydro-thermal reaction is 2-30MPa, preferably 5-20MPa；
Preferably, the time of step (3) the secondary hydro-thermal reaction is 2-20h, preferably 5-12h.
8. the method according to claim 1 to 7, which is characterized in that the temperature of step (4) described heat treatment is 500-
1000 DEG C, preferably 700-900 DEG C；
Preferably, the time of step (4) described heat treatment is 0.5-10h, preferably 1-4h.
9. the molybdenum sulfide flexible electrode material that the method according to claim 1 is prepared.
10. the application of molybdenum sulfide flexible electrode material as claimed in claim 9, which is characterized in that the molybdenum sulfide flexible electrical
Pole material is used as lithium ion battery negative material, anode material of lithium-ion battery, electrode material for super capacitor or liberation of hydrogen material.
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| CN113539698A (en) * | 2021-07-09 | 2021-10-22 | 南京大学 | Zinc/nitrogen/sulfur co-doped carbon material composite material and preparation method and application thereof |
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