CN110474050A - A kind of doping type carbon/manganese sulfide composite material and preparation method thereof - Google Patents
A kind of doping type carbon/manganese sulfide composite material and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to manganese sulfide technical field of composite materials, more particularly to a kind of doping type carbon/manganese sulfide composite material and preparation method thereof, it is specific as follows: inorganic nitrate being dissolved in the acid solution containing the concentrated sulfuric acid, original carbon material is then separately added into and permanganate carries out oxidation reaction.After reaction, reducing agent and non-oxidizable strong acid are sequentially added into reaction solution, are carried out stratification processing after being sufficiently stirred again, are obtained lower sediment thing.It is added into the sediment and contains heteroatomic molecular source, through high-temperature heat treatment, doping type carbon/manganese sulfide composite material is finally made.The invention has the following beneficial effects: be based on raw material optimum use theory, during carbon material Oxidation Doping, manganese/sulphur particle of carbon material oxidation reaction remaining is made full use of, directly heat treatment obtains doping type carbon/manganese sulfide composite material, reduces the wasting of resources and environmental pollution；Whole preparation process simple process, reaction raw materials utilization rates be high and nanocomposite constituents are uniformly dispersed, quality more preferably.
Description
Technical field
The present invention relates to manganese sulfide technical field of composite materials more particularly to a kind of doping type carbon/manganese sulfide composite materials
Preparation method.
Background technique
The energy and environment are two big hot spots of 21 century mankind concern.Not with the non-renewable fossil fuel such as coal and petroleum
Disconnected consumption and therewith bring problem of environmental pollution, are increasingly becoming the bottleneck of social development, seeking and develop novel green can
The renewable sources of energy become the breach of human kind sustainable development.But there is interval in the renewable energy of the forms such as wind energy, solar energy
Property, dispersibility the problems such as, using based on electrochemistry energy storage and reforming unit realize that such renewable energy efficiently utilizes
It is crucial.
Lithium ion battery as a kind of novel energy storage apparatus, because its energy density is high, have extended cycle life the advantages that by pass
Note.To promote and optimizing battery performance, select suitable electrode material most important.Graphite has been carried out as negative electrode material
The commercial applications of lithium ion battery.Nevertheless, graphite-phase limits lower theoretical specific capacity (only 372 mAh/g)
The application of its wider scope.Manganese sulfide is as a kind of new material, because its higher theoretical specific capacity (616 mAh/g) is considered as
The excellent candidate of cathode of lithium battery.
Alkaline fuel cell is as another kind of electrochemical energy storage device, because of its energy conversion efficiency high (up to 100%), electricity
Pole active material can the advantages such as continuous supplementation also attracted the interest of numerous researchers.Redox reactions are as basic fuel electricity
The key reaction of pond anode selects suitable oxygen reduction catalyst significant for promoting its overall performance.Manganese sulfide is because of it
Preferable oxygen catalytic activity and electric conductivity more superior than manganese-base oxide, are considered as very promising oxygen reduction catalyst.
Based on above-mentioned analysis, manganese sulfide shows potential application prospect in lithium cell negative pole and hydrogen reduction catalytic field.
Patent CN201210332066.1 discloses a kind of high-purity manganese sulfide and preparation method thereof, includes the following steps: (1)
Pre-treatment step: manganese sulfide is added in manganese sulfate solution, rear to be separated by solid-liquid separation；(2) it sprays reaction step: being obtained in step (1)
To solution in, be added liquefied ammonia obtain spray liquid, by spray liquid by circulating pump carry out circulated sprinkling, with hydrogen sulfide gas progress
Circulated sprinkling reaction；Until manganese ion mass concentration is less than 500ppm, end spray reaction in reaction solution；By spray reaction knot
Solution after beam is separated by solid-liquid separation；(3) washing and drying obtain vulcanization manganese product.
But the waste material generated in production process can not be recycled or is recycled, waste of resource simultaneously causes environment
Certain harm, and simple manganese sulfide remain poorly conductive, it is easy to reunite, stability is poor the problems such as, hinder its business
Change application and a wide range of popularization in market.Manganese sulfide and doping type carbon are carried out compound to be proved to be having of solving the above problems
Effect strategy.On the one hand, compound with doping type carbon, it can significantly promote the electric conductivity of manganese sulfide；On the other hand, using carbon material compared with
Big specific surface area and good mechanicalness and flexibility can be dispersed, coat and stablize manganese sulfide, and then effectively inhibit its group
It is poly-, enhance its stability.
Patent CN201711306796.3 discloses a kind of preparation method of manganese sulfide/carbon nano tube compound material, specifically
It is to be added to carbon nanotube in the mixed acid that the concentrated sulfuric acid and concentrated nitric acid are prepared to carry out ultrasonication, connects carbon nano tube surface
Then hydrophilic radical on branch mixes it with surfactant, form suspension, add the sulphur source with amino, make it
It reacts with the group in carbon nanotube, is then mixed into manganese source wherein, and be transferred in reaction kettle and carry out hydro-thermal reaction, obtain sulphur
Change manganese/carbon nano tube compound material.
But it remains following disadvantage: synthesis process is comparatively laborious, and respectively reacts remaining waste material step by step
It is wasted, can not recycle or be recycled, be easy to cause the waste of resource and the pollution of environment；Manufacturing cost is higher, it is difficult to
It realizes and promotes on a large scale.Thus, design that a kind of simple process, reaction raw materials utilization rate are high, reduce pollution and component dispersion is equal
Even doping type carbon/manganese sulfide composite material and preparation method thereof fires exploitation high performance lithium ionic cell cathode material and alkalinity
Material anode catalyst has great importance.
Summary of the invention
It is a primary object of the present invention to overcome deficiency in the prior art, it is compound to provide a kind of doping type carbon/manganese sulfide
Material preparation method.It is excellent that the preparation method has that synthesis technology is simple, reaction raw materials utilization rate is high, material component is uniformly dispersed etc.
Point.
To achieve the purpose of the present invention, the following technical schemes are provided:
A kind of doping type carbon/manganese sulfide composite material and preparation method thereof, includes the following steps:
(1) 0.5~1.0 g inorganic nitrate is dissolved in 40~60 mL concentrated sulfuric acids or mixed acid liquid containing the concentrated sulfuric acid, is formed strong
Oxidisability chemical environment；The original carbon material of 1.0~1.5 g is added, 20~30 min are stirred under the conditions of 0~5 DEG C, are mixed
Close liquid；
(2) 4~5 g permanganates are added into step (1) resulting mixed liquor, further enhance the oxidation characteristic of mixed liquor,
Manganese source is also introduced into reaction solution simultaneously；10~15 min are stirred, are then heated to 35~45 DEG C, reaction 20~30
h；
(3) 400~500 mL deionized waters are added into step (2) resulting reaction solution and are diluted processing, then successively add
Enter reducing agent and concentrated hydrochloric acid, 2~3 h are sufficiently stirred；Reducing agent, which is added, can be reduced into septivalency manganese in solution bivalent manganese, be added dense
It is conducive to subsequent solution after hydrochloric acid to be layered, accelerates reaction process；
(4) the resulting reaction solution of step (3) is stood 1~2 day, solution layering removes supernatant liquor, is separated by filtration to obtain down
Layer sediment；
(5) the resulting sediment of step (4) is dried, and is mixed with 1:5~1:10 in mass ratio containing heteroatomic molecular source
It closes, is then heat-treated 2~3 h at 700~900 DEG C under an inert atmosphere, doping type carbon/manganese sulfide composite wood can be obtained
Material.Wherein, carbon material is oxidation-treated, and defect is rich in structure, can realize doping vario-property under heat treatment condition；Meanwhile two
Valence manganese serves as manganese source, and sulfate radical can be reduced into negative divalent sulfur by carbon material under high temperature atmosphere, serves as sulphur source, and then react and formed
Manganese sulfide.
Preferably, the inorganic nitrate is one of sodium nitrate, potassium nitrate, lithium nitrate, zinc nitrate or a variety of mixing
Object.
Preferably, the mixed acid liquid containing the concentrated sulfuric acid is the concentrated sulfuric acid/nitric acid mixed liquor or the concentrated sulfuric acid/phosphoric acid mixed liquor.
Preferably, the original carbon material is one of carbon nanotube, graphite, carbon fiber, biomass carbon or a variety of mixed
Close object.
Preferably, the permanganate is one of potassium permanganate, sodium permanganate, high manganese lithium, zinc permanganate or more
Kind mixture.
Preferably, the reducing agent is hydrogen peroxide, sulfurous acid, sulfur dioxide or sulphur powder.
Preferably, described to include the molecular source of nitrogen atom, the molecular source containing boron atom containing heteroatomic molecular source and contain
The molecular source of phosphorus atoms；Wherein, the molecular source of nitrogen atom is one of urea, melamine, cyanamide, dicyandiamide or more
Kind mixture；Molecular source containing boron atom is one in boric acid, diboron trioxide and 1- ethyl-3-methylimidazole tetrafluoroborate
Kind or a variety of mixtures；Molecular source containing phosphorus atoms be one of thiocarbamide, thioacetamide, vulcanized sodium and benzyl disulfide or
A variety of mixtures.
The invention has the following beneficial effects:
(1) composite material preparation process is simple, and reaction raw materials utilization rate is high, saves manufacturing cost, reduces material to a certain extent
The problem of problem of environmental pollution and waste of raw materials for may cause in material synthesis process, convenient for large-scale production and market
A wide range of popularization；
(2) manganese sulfide particle with nanoscale is anchored on carbon material surface and interface, is uniformly dispersed, reunites in the composite material obtained by
Effect obviously weakens, and can effectively expose its catalysis, storage lithium site, and then show excellent storage lithium characteristic and oxygen catalytic performance,
Product quality is more preferably.
Detailed description of the invention
Fig. 1 is the XRD diagram of NSCNT/NSG/MnS composite material prepared by embodiment 1.
Fig. 2 is the TEM figure (a) and element mapping figure (b) of NSCNT/NSG/MnS composite material prepared by embodiment 1.
Fig. 3 is the nitrogen adsorption desorption curve (a) and pore-size distribution of NSCNT/NSG/MnS composite material prepared by embodiment 1
Curve (b).
Fig. 4 is the total spectrogram (a) of XPS and the S2p high-resolution spectrogram of NSCNT/NSG/MnS composite material prepared by embodiment 1
(b).
Fig. 5 is the negative electrode of lithium ion battery circulation (a) and multiplying power of NSCNT/NSG/MnS composite material prepared by embodiment 1
(b) performance map.
Fig. 6 a is NSCNT/NSG/MnS composite material prepared by embodiment 1 and commercialization Pt/C, and catalyst is in revolving speed
Linear scan curve under the conditions of 1600 rpm；Fig. 6 b is the NSCNT/NSG/MnS composite material of the preparation of embodiment 1 in current potential
For the K-L curve under the conditions of -0.8 V.
Fig. 7 is nitrogen sulphur codope carbon nanotube/manganese sulfide composite material (NSCNT/MnS) XRD prepared by embodiment 2
Figure.
Specific embodiment
In the description of the present invention, it should be noted that term " center ", "upper", "lower", "left", "right", "vertical",
The orientation or positional relationship of the instructions such as "horizontal", "inner", "outside" is to be based on the orientation or positional relationship shown in the drawings, or be somebody's turn to do
Invention product using when the orientation or positional relationship usually put, be merely for convenience of description of the present invention and simplification of the description, without
It is that the device of indication or suggestion meaning or element must have a particular orientation, is constructed and operated in a specific orientation, therefore not
It can be interpreted as limitation of the present invention.In addition, term " first ", " second ", " third " etc. are only used for distinguishing description, and cannot manage
Solution is indication or suggestion relative importance.
In the description of the present invention, it is also necessary to which explanation is unless specifically defined or limited otherwise, term " setting ",
" installation ", " connected ", " connection " shall be understood in a broad sense, for example, it may be fixedly connected, may be a detachable connection or one
Connect to body；It can be mechanical connection, be also possible to be electrically connected；It can be directly connected, it can also be indirect by intermediary
It is connected, can be the connection inside two elements.For the ordinary skill in the art, on being understood with concrete condition
State the concrete meaning of term in the present invention.
In order to make the objectives, technical solutions and advantages of the present invention clearer, below by accompanying drawings and embodiments, to this
Invention is further elaborated.However, it should be understood that the specific embodiments described herein are merely illustrative of the present invention,
The range being not intended to restrict the invention.In addition, in the following description, descriptions of well-known structures and technologies are omitted, to keep away
Exempt from unnecessarily to obscure idea of the invention.
Embodiment 1
The concentrated sulfuric acid of 70% concentration of 0.5 g sodium nitrate and 45 mL is taken to be placed in 250 mL round-bottomed flasks, (0 under condition of ice bath
DEG C or so) it is successively slowly added to 0.5 g multi-walled carbon nanotube and 0.5 g graphite powder, after stirring 20 min, it is uniformly mixed
Liquid；5 g potassium permanganate are added into above-mentioned mixed liquor, after stirring 10 min, is warming up to 40 DEG C, after reacting 24 h, will react
Product is transferred in 1 L beaker, and deionized water is added to be diluted to 500 mL, adds 5 mL hydrogen peroxide (30%), adds 50 with subsequent
The concentrated hydrochloric acid of 30% concentration of mL, is sufficiently stirred 2 h.After the reaction solution is stood 1 day, solution realizes obvious layering, removes upper layer
Clear liquid obtains lower sediment thing.After the sediment of acquisition is dried, 1:6 is mixed with urea in mass ratio, in nitrogen atmosphere
800 DEG C of 2 h of calcining, finally obtain nitrogen sulphur codope carbon nano tube/graphene/manganese sulfide composite material (NSCNT/NSG/
MnS).
Refering to fig. 1, the XRD diagram of the NSCNT/NSG/MnS composite material prepared as shown in the figure, as seen from the figure, 2 θ=
Occur apparent MnS characteristic diffraction peak at 29.6 °, 34.3 °, 49.3 °, 61.4 ° and 82.5 °, successfully synthesizes MnS.
Referring to Fig.2, the TEM figure (a) and element mapping of the NSCNT/NSG/MnS composite material prepared as shown in the figure are schemed
(b), by Fig. 2 a it is found that there are tri- kinds of components of NSCNT, NSG and MnS in the composite material.By Fig. 2 b it is found that N element and C element
Distribution situation is consistent, shows that carbon material is successfully realized and mixes N；It finding simultaneously, S element can not only form MnS with Mn element, but also
Part S atom also mixes in carbon skeleton.
Refering to Fig. 3, the nitrogen adsorption desorption curve (a) of the NSCNT/NSG/MnS composite material prepared as shown in the figure and aperture
Distribution curve (b), by Fig. 3 a it is found that the nitrogen adsorption desorption curve of the composite material belongs to the IVth seed type, and with typical case
Capillary condensation phenomenon, show its unique porosity, increase and electro-chemical activity surface and increase the storage of lithium ion
Capacity.By Fig. 3 b it is found that the composite material apparent characteristic peak occurs in about 38 nm, it was demonstrated that its mesoporous characteristic.
Refering to Fig. 4, the total spectrogram (a) of the XPS of the NSCNT/NSG/MnS composite material prepared as shown in the figure and S 2p high-resolution
Spectrogram (b), by Fig. 4 a it is found that there are five kinds of elements of C, O, N, Mn and S in the composite material, it was demonstrated that be likely to form MnS.By Fig. 4 b
It is found that occurring the characteristic peak of S-S/S-C at 163.8 eV and 164.8, show that S has been mixed in carbon skeleton；Discovery exists simultaneously
There is the characteristic peak of Mn-S/C-S-Mn at 161.0 eV and 162.1 eV, illustrates that there are MnS in composite material.
Refering to Fig. 5, the negative electrode of lithium ion battery of the NSCNT/NSG/MnS composite material prepared as shown in the figure circulation (a) and
Multiplying power (b) performance map, by Fig. 5 a it is found that the composite material recycles 150 circles under 0.2A/g current density, specific discharge capacity is still super
Cross 800mAh/g；And 450 circle of circulation under 0.5A/g current density, specific discharge capacity remain to stablize in 600mAh/g, it was demonstrated that its
Excellent cyclical stability；By figure b it is found that when discharge current density is promoted to 1.6A/g from 0.1A/g, the composite material
Specific discharge capacity is still up to 400mAh/g, it was demonstrated that cyclical stability and high rate performance of the composite material under each current density are good
It is good.
Refering to Fig. 6, the NSCNT/NSG/MnS composite material and commercialization Pt/C catalyst prepared as shown in the figure is in revolving speed
Linear scan curve under the conditions of 1600 rpm；Fig. 6 b is the NSCNT/NSG/MnS composite material of the preparation of embodiment 1 in current potential
It for the K-L curve under the conditions of -0.8 V, can be seen that from Fig. 6 a, NSCNT/NSG/MnS's plays spike potential (0.02V) than business
Pt/C electrode (- 0.02V) corrigendum, and its limiting current density is suitable with Pt/C, it was demonstrated that its excellent oxygen catalytic activity.By scheming
6b shows that its surface and interface occurs it is found that the transfer electron number that measures under -0.8 V current potential of NSCNT/NSG/MnS electrode is 3.97
Hydrogen reduction process be about four electronic transfer process.
Embodiment 2
The concentrated sulfuric acid of 70% concentration of 0.5 g potassium nitrate and 45 mL is taken to be placed in 250 mL round-bottomed flasks, (0 under condition of ice bath
DEG C or so) it is slowly added to 1 g multi-walled carbon nanotube, after stirring 20 min, be uniformly mixed liquid；It is added into above-mentioned mixed liquor
5 g potassium permanganate after stirring 15 min, are warming up to 40 DEG C, after reacting 20 h, reaction product are transferred in 1 L beaker, is added
Deionized water is diluted to 500 mL, adds 5 mL hydrogen peroxide (30%), with subsequent plus 50 mL, 30% concentration concentrated hydrochloric acid, fills
Divide stirring 2 h.After the reaction solution is stood 1 day, solution realizes obvious layering, removes supernatant liquor, obtains lower sediment thing.It will
After the sediment drying of acquisition, 1:10 is mixed with urea in mass ratio, and 800 DEG C of 2 h of calcining, finally obtain in nitrogen atmosphere
Nitrogen sulphur codope carbon nanotube/manganese sulfide composite material (NSCNT/MnS).
Refering to Fig. 7, nitrogen sulphur codope carbon nanotube/manganese sulfide composite material (NSCNT/MnS) for preparing as shown in the figure
There is apparent MnS characteristic diffraction peak as seen from the figure at 2 θ=29.6 °, 34.3 °, 49.3 °, 61.4 ° and 82.5 ° in XRD diagram,
Proof successfully synthesizes MnS.
It should be noted that being not intended to limit although the various embodiments described above have been described herein
Scope of patent protection of the invention.Therefore, it based on innovative idea of the invention, change that embodiment described herein is carried out and is repaired
Change, or using equivalent structure or equivalent flow shift made by description of the invention and accompanying drawing content, it directly or indirectly will be with
Upper technical solution is used in other related technical areas, is included within the scope of protection of the patent of the present invention.
Claims (7)
1. a kind of doping type carbon/manganese sulfide composite material and preparation method thereof, characterized by the following steps:
(1) 0.5~1.0 g inorganic nitrate is dissolved in 40~60 mL concentrated sulfuric acids or mixed acid liquid containing the concentrated sulfuric acid, is added
The original carbon material of 1.0~1.5 g stirs 20~30 min under the conditions of 0~5 DEG C, obtains mixed liquor；
(2) 4~5 g permanganates are added into step (1) resulting mixed liquor, stir 10~15 min, subsequent heat temperature raising
To 35~45 DEG C, 20~30 h are reacted；
(3) 400~500 mL deionized waters are added into step (2) resulting reaction solution and are diluted processing, then successively add
Enter reducing agent and concentrated hydrochloric acid, 2~3 h are sufficiently stirred；
(4) the resulting reaction solution of step (3) is stood 1~2 day, solution layering removes supernatant liquor, is separated by filtration to obtain down
Layer sediment；
(5) the resulting sediment of step (4) is dried, and is mixed with 1:5~1:10 in mass ratio containing heteroatomic molecular source
It closes, is then heat-treated 2~3 h under the conditions of 700~900 DEG C under an inert atmosphere, it is multiple that doping type carbon/manganese sulfide can be obtained
Condensation material.
2. a kind of doping type carbon/manganese sulfide composite material and preparation method thereof according to claim 1, it is characterised in that:
The inorganic nitrate is one of sodium nitrate, potassium nitrate, lithium nitrate, zinc nitrate or a variety of mixtures.
3. a kind of doping type carbon/manganese sulfide composite material and preparation method thereof according to claim 1, it is characterised in that:
The mixed acid liquid containing the concentrated sulfuric acid is the concentrated sulfuric acid/nitric acid mixed liquor or the concentrated sulfuric acid/phosphoric acid mixed liquor.
4. a kind of doping type carbon/manganese sulfide composite material and preparation method thereof according to claim 1, it is characterised in that:
The original carbon material is one of carbon nanotube, graphite, carbon fiber, biomass carbon or a variety of mixtures.
5. a kind of doping type carbon/manganese sulfide composite material and preparation method thereof according to claim 1, it is characterised in that:
The permanganate is one of potassium permanganate, sodium permanganate, high manganese lithium, zinc permanganate or a variety of mixtures.
6. a kind of doping type carbon/manganese sulfide composite material and preparation method thereof according to claim 1, it is characterised in that:
The reducing agent is hydrogen peroxide, sulfurous acid, sulfur dioxide or sulphur powder.
7. a kind of doping type carbon/manganese sulfide composite material and preparation method thereof according to claim 1, it is characterised in that:
Described containing heteroatomic molecular source includes the molecular source of nitrogen atom, the molecular source containing boron atom and containing the molecule of phosphorus atoms
Source；
The molecular source of the nitrogen atom is one of urea, melamine, cyanamide, dicyandiamide or a variety of mixtures；
The molecular source containing boron atom is one of boric acid, diboron trioxide, 1- ethyl-3-methylimidazole tetrafluoroborate
Or a variety of mixtures；
The molecular source containing phosphorus atoms is one of thiocarbamide, thioacetamide, vulcanized sodium, benzyl disulfide or a variety of mixing
Object.
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| CN114937761A (en) * | 2022-04-25 | 2022-08-23 | 多助科技(武汉)有限公司 | Nobaltosulfide/manganese sulfide/nitrogen-carbon composite material and preparation method and application thereof |
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