CN108666570A - Porous carbon nanobelts lithium sulfur battery anode material and its preparation method and application - Google Patents
Porous carbon nanobelts lithium sulfur battery anode material and its preparation method and application Download PDFInfo
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- CN108666570A CN108666570A CN201810335294.1A CN201810335294A CN108666570A CN 108666570 A CN108666570 A CN 108666570A CN 201810335294 A CN201810335294 A CN 201810335294A CN 108666570 A CN108666570 A CN 108666570A
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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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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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
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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
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a kind of porous carbon nanobelts lithium sulfur battery anode materials and preparation method thereof and lithium-sulphur cell positive electrode, lithium-sulfur cell.The porous carbon nanobelts lithium sulfur battery anode material preparation method comprises the step of：Prepare carbon nanobelts presoma；Charing and activation process are carried out to carbon nanobelts presoma；Sulphur simple substance is deposited in the porous carbon nanobelts of the nitrogen oxygen codope.Porous carbon nanobelts lithium sulfur battery anode material prepared by preparation method of the present invention has large specific surface area, the content of good wetability and high elemental sulfur, and significantly improves sulfur fixation performance, effectively inhibits the chemical properties such as " the shuttle effect " of polysulfide.The lithium-sulphur cell positive electrode, lithium-sulfur cell contain the lithium sulfur battery anode material of the method for the present invention preparation.
Description
Technical field
The present invention relates to electrode material technical fields, and in particular to a kind of porous carbon nanobelts lithium sulfur battery anode material and
Preparation method and application.
Background technology
The main problem that energy problem will be the mankind to be faced in future, the resources such as current oil, coal mine are increasingly deficient, and
Development process consumption is big, seriously polluted, therefore each state, all in the clean energy resource for greatly developing sustainable use, this just be unable to do without energy
The storage and management in source.And energy storage material plays very important effect in energy storage and management aspect.Secondary cell is mesh
Preceding the most widely used energy storage device, wherein lithium ion battery due to higher energy density (150-200Wh/kg) and
Preferable cyclical stability occupies main market.However as current lithium ion battery actual energy density very
Close to its theoretical energy density, it is difficult to generate huge breakthrough.
Lithium-sulfur cell is the lithium metal conduct using element sulphur as anode as a kind of novel energy storage device
A kind of lithium battery of cathode.Elemental sulfur rich reserves in the earth have the characteristics that cheap, environmental-friendly.Made using sulphur
For the lithium-sulfur cell of positive electrode, materials theory specific capacity and battery theory are higher than energy, respectively reach 1675m Ah/g
And 2600Wh/kg, significantly larger than commercial widely applied cobalt acid lithium battery capacity (<150mAh/g).And sulphur is a kind of
Environment amenable element does not pollute environment substantially, is a kind of very promising lithium battery, in communications and transportation, electronics
The fields such as information, defence and military and aerospace have broad application prospects.
Although lithium-sulfur cell has many advantages, such as, compared to lithium ion battery, lithium-sulfur cell still faces as follows at present
Main problem：Poor cycle performance and faster energy attenuation.It is mainly manifested in：The electric conductivity of sulphur itself is excessively poor；It is filling
The volume of sulphur can change during electric discharge, and then crack and fall off from electrode；Along with more vulcanizations in charge and discharge process
" the shuttle effect " of object, influences the service life of battery；The self discharge of polysulfide makes battery capacity decaying very fast.So reason
The sulfur electrode thought should include four features：(1) there is the volume expansion of enough space sulphur；(2) good electronic conductivity
With lithium ion transport channel；(3) possess higher specific surface area, to keep the shape of electrode；(4) pass through physics and chemical means
Effective capture polysulfide.
Various materials are used to improve the performance of sulphur anode, and wherein electric conductivity is preferable, specific surface area and pore volume
Larger carbon material is considered as very promising lithium sulfur battery anode material.Carbon-based material, such as current use are relatively more
Activated carbon, carbon nanotube, carbon nano-fiber and graphene etc. suffer from excellent electric conductivity, pass through answering for carbon material and sulphur
It closes, the electric conductivity of lithium sulfur battery anode material can be made to greatly improve, simultaneously because the adsorptivity of carbon can also reduce polysulfide
Dissolving.Wherein, activated carbon is most materials of research, and is the widest carbon materials used in ultracapacitor etc.
Material, because it is easily prepared, the high and lower production cost of specific surface area, but there are excessive micropores for activated carbon, and its aperture
It is relatively simple, thus specific surface area utilization rate is extremely limited, affects the diffusion and transmission of electronics and ion, reduces such as lithium sulphur electricity
The performance in pond.Carbon fiber has excellent electric conductivity and can not use binder, but its apparent density is relatively low, volume ratio electricity
Rong Bugao, and it is expensive.Though carbon nanotube has excellent electric conductivity and mechanical performance, such as there is hierarchical porous structure aperture,
System easy to control in size, but relatively small specific surface area, and the production of carbon nanotube is relatively complicated, production cost is higher.Graphene
It is to be considered a kind of very promising material in recent years, it has good electric conductivity, larger specific surface area and can
The pore size of control, but graphene is very easy to reunite, its performance is made to have a greatly reduced quality.
Additionally due to the hydrophobicity of existing carbon material inherently so that specific surface area utilization rate is not high.Therefore, will work as
Preceding carbon material will realize that good high rate performance, cycle performance are excellent still with the compound positive electrode applied to lithium-sulfur cell of sulphur
It is so a huge challenge.
Invention content
It is an object of the invention to overcome the above-mentioned deficiency of the prior art, a kind of porous carbon nanobelts lithium-sulfur cell is being provided just
Pole material and preparation method thereof, it is undesirable with the high rate performance and cycle performance that solve existing carbon containing lithium sulfur battery anode material
Technical problem.
Another object of the present invention is to provide a kind of lithium-sulphur cell positive electrode and lithium-sulfur cells, to solve existing lithium-sulfur cell
Anode and lithium-sulfur cell cause the technology of lithium-sulfur cell high rate performance and poor circulation to be asked due to lithium sulphur positive electrode
Topic.
In order to achieve the above-mentioned object of the invention, an aspect of of the present present invention is providing a kind of porous carbon nanobelts lithium-sulfur cell just
The preparation method of pole material.The porous carbon nanobelts lithium sulfur battery anode material preparation method includes the following steps：
Formaldehyde, hydroquinone are subjected to hydro-thermal reaction in an acidic solution, obtain carbon nanobelts presoma；
By the carbon nanobelts presoma through charing process and ammonium hydroxide activation process, the porous carbon for obtaining nitrogen oxygen codope is received
Rice band；
After the porous carbon nanobelts and elemental sulfur are carried out mixture, it is heat-treated in closed environment so that institute
Elemental sulfur is stated to volatilize and be deposited in the porous carbon nanobelts.
Another aspect of the present invention provides a kind of porous carbon nanobelts lithium sulfur battery anode material.The porous carbon is received
Rice band lithium sulfur battery anode material is to be prepared by the porous carbon nanobelts lithium sulfur battery anode material preparation method of the present invention.
Another aspect of the invention provides a kind of lithium-sulphur cell positive electrode.The lithium-sulphur cell positive electrode include collector and
The positive-active layer being incorporated on the collector, the positive-active layer include sulphur positive electrode, conductive agent and binder,
In, the sulphur positive electrode is lithium sulphur positive electrode of the present invention.
Another aspect of the present invention provides a kind of lithium-sulfur cell.The lithium-sulfur cell include anode and cathode, it is described just
Lithium-sulphur cell positive electrode extremely of the present invention.
Compared with prior art, the porous carbon nanobelts lithium sulfur battery anode material preparation method of the present invention is by charing process institute
The carbon nanobelts of generation carry out ammonium hydroxide activation process, to introduce nitrogenous and oxygen containing functional group on carbon nanobelts, effectively change
The wetability of kind carbon nanobelts, improves carbon nanobelts specific surface area utilization rate.Meanwhile it being received by the porous carbon that ammonium hydroxide activates
Rice contains the porous structure in multistage aperture with lithium sulfur battery anode material, and therefore, the porous carbon nanobelts lithium-sulfur cell of generation is just
Pole material specific surface area is big, and the porous structure multi-stage porous can also play synergy, improve the content of elemental sulfur.Therefore,
Porous carbon nanobelts lithium sulfur battery anode material prepared by preparation method of the present invention has large specific surface area, good wetability
With the content of high elemental sulfur, and sulfur fixation performance is significantly improved, effectively inhibits the chemical properties such as " shuttle effect " of polysulfide.
In addition, preparation method technique of the present invention is relatively easy, condition is easily-controllable, efficient, prepares porous carbon nanobelts lithium-sulphur cell positive electrode
Material property is stablized.
The porous carbon nanobelts lithium sulfur battery anode material of the present invention has a porous structure, and surface nitrogen-containing functional group and contains
Oxygen official, and sulphur simple substance can uniform deposition inside and outside the porous structure of the hollow carbon nanometer micro ball of nitrogen oxygen doping.Therefore, described
Porous carbon nanobelts lithium sulfur battery anode material have large specific surface area, the content of good wetability and high elemental sulfur, and
Sulfur fixation performance is significantly improved, the chemical properties such as " the shuttle effect " of polysulfide are effectively inhibited.
Lithium-sulphur cell positive electrode and lithium-sulfur cell of the present invention due to containing lithium sulfur battery anode material of the present invention, it is described
Lithium-sulphur cell positive electrode and lithium-sulfur cell not only have higher specific capacitance, but also also good high rate performance and stable circulation
Property.
Description of the drawings
Fig. 1 is the scanning electron microscopic picture (SEM) of carbon nanobelts presoma prepared by the embodiment of the present invention 1；
Fig. 2 is the scanning electron microscopic picture (SEM) of the porous carbon nanobelts of nitrogen oxygen codope prepared by the embodiment of the present invention 1；
Fig. 3 is the physical absorption curve (BET) of the hollow carbon nanometer micro ball of N doping prepared by the embodiment of the present invention 1；
Fig. 4 is the pore size distribution curve of the hollow carbon nanometer micro ball of N doping prepared by the embodiment of the present invention 1；
Fig. 5 is the X-ray photoelectron spectroscopic analysis image of the hollow carbon nanometer micro ball of N doping prepared by the embodiment of the present invention 1
(XPS)。
Specific implementation mode
In order to make technical problems, technical solutions and advantageous effects to be solved by the present invention be more clearly understood, below in conjunction with
Embodiment, the present invention will be described in further detail.It should be appreciated that specific embodiment described herein is only used to explain
The present invention is not intended to limit the present invention.
Unless otherwise defined, otherwise all technical terms and scientific terms used herein have and institute of the embodiment of the present invention
Belong to technical field those of ordinary skill and is generally understood identical meaning.If the definition stated in this part be incorporated by reference
The definition stated in the patent of this paper, patent application, the patent application of announcement and other publications is opposite or other aspects
Inconsistent, the definition listed in this part is prior to the definition in being totally incorporated herein by reference.
In addition, the quality of Related Component noted in the disclosure of the embodiment of the present invention not only may refer to each component
Concrete content can also indicate the proportionate relationship of quality between each component, therefore, as long as according to specification phase of the embodiment of the present invention
The content for closing component is scaled up or is reduced within specification of embodiment of the present invention scope of disclosure.Specifically, this hair
Bright embodiment quality described in the specification can be mass unit well known to the chemical fields such as μ g, mg, g, kg.
On the one hand, the embodiment of the present invention provides a kind of preparation method of porous carbon nanobelts lithium sulfur battery anode material.Institute
The preparation method for stating porous carbon nanobelts lithium sulfur battery anode material includes the following steps：
Step S01. prepares carbon nanobelts presoma：
Formaldehyde, hydroquinone are subjected to hydro-thermal reaction in an acidic solution, obtain carbon nanobelts presoma；
Step S02. carries out charing and activation process to carbon nanobelts presoma：
By the carbon nanobelts presoma through charing process and ammonium hydroxide activation process, the porous carbon for obtaining nitrogen oxygen codope is received
Rice band；
Sulphur simple substance is deposited in the porous carbon nanobelts of the nitrogen oxygen codope by step S03.：
After the porous carbon nanobelts of the nitrogen oxygen codope and elemental sulfur are carried out mixture, heat is carried out in closed environment
Processing so that the elemental sulfur volatilizees and is deposited in the porous carbon nanobelts.
Wherein, in step S01, the polymerisation that reaction formaldehyde carries out in an acidic solution with hydroquinone generates ladder band
The polymer of shape.Hydro-thermal reaction chemical formula between the formaldehyde and hydroquinone is as follows：
In the reaction system, there is nano strip in the product of generation, as shown in Figure 1.
In one embodiment, the temperature of the hydro-thermal reaction in step S01 is 120-200 DEG C, reaction time 8-
16h.In another embodiment, the mass ratio of the formaldehyde and the hydroquinone is (1-5)：(1-4)；The acid solution with
The mass ratio of the hydroquinone is (50-150)：(1-4).Preferably, the matter of the acid solution and formaldehyde and hydroquinone
Amount is than being (50-100)：(1-4)：(1-3).In a particular embodiment, it can be 5%- that the acid solution, which selects mass concentration,
The concentration of 20% dilute hydrochloric acid, the formalin may be 30%-40%, and such as 37%.In this way, by hydro-thermal reaction body
System is such as specifically to reactant concentration ratio, reaction dissolvent and hydrothermal temperature and time factor controlling and adjusting, a side
The reaction efficiency of reactant is improved in face, improves the yield of product；On the other hand so that product can crystallize the band-like carbon of precipitation and receive
Rice band presoma.
In above-mentioned steps S02, charing process can be conventional charing process, that is to say the institute that will be prepared in step S01
Carbon nanobelts presoma thermal cracking is stated, to which organic cracking is generated carbon.In one embodiment, the temperature of the charing process
It can be 700-1000 DEG C.In addition charing process should be sufficient, such as in one embodiment, be heat-treated at 700-1000 DEG C
Time be 20-120min so that above-mentioned carbon nanobelts presoma fully carbonizes.In addition, control the heat treatment temperature be with
Heating rate is that 2-10 DEG C/min is warming up to 700-1000 DEG C.In this way, by the control of heating rate, ensure the carbon that charing generates
Nanobelt form it is complete, and have porous structure.
In one embodiment, the ammonium hydroxide activation process is so that the carbon nanobelts for the porous structure that charing generates are being protected
In property atmosphere, it is heat-treated at 700-1000 DEG C；And the protective atmosphere contains the ammonia thermally decomposed to generate by ammonium hydroxide
The mixed gas of gas and vapor.Activation process is carried out to porous carbon nanobelts by ammonia so that generated in charing porous
Generate abundant nitrogenous and oxygen-containing functional group on carbon nanobelts, the presence of nitrogen-containing functional group and oxygen-containing functional group can increase additional
Faraday pseudo-capacitance improves wetability of the porous carbon nanobelts to electrolyte, improves its specific surface utilization rate, reduces electrolysis
Diffusional resistance of the liquid intermediate ion in material duct can provide lone pair electrons, increase the transmission rate of electronics in the material, inhale
Draw electrolyte intermediate ion and improve electric double layer concentration, increases the chemical property of material.
In a preferred embodiment, the method for the charing process and ammonium hydroxide activation process is as follows：
It, will treated that the carbon nanobelts presoma carries out heat at 700-1000 DEG C through dusting in protective atmosphere
Processing；And the protective atmosphere contains the mixed gas of the ammonia and vapor that are thermally decomposed to generate by ammonium hydroxide.
It is handled in same atmosphere in this way, being arranged charing process and activation process, can not only make charing process
Abundant nitrogenous and oxygen-containing functional group is generated on the porous carbon nanobelts generated, improves its wetability and related chemical property；
On the other hand, additionally it is possible to the porous structure on its surface is effectively improved, so that the hole of its porous structure is with gradient pore
Diameter, such as containing micropore, mesoporous and macropore hierarchical porous structure, certainly, the porous structure of this different pore size is random distribution
, the porous structure of this porous pore-size distribution can synergistic effect for promoting porous carbon nanobelts lithium sulfur battery anode material
Chemical property, such as electrode material for super capacitor when, specific capacity, high rate performance and cyclical stability can be improved
Etc. performances.
In addition, the protective atmosphere of above-mentioned charing or activation process can be provided by argon gas, into the protective atmosphere
The ammonia and water vapour for being passed through the heated volatilization of ammonia can be imported with argon gas.As in one embodiment, the flow of the argon gas can
To be set as 20-150ml/min, the ammonia and water vapour of the volatilization of ammonium hydroxide should be enough, can such as be added ammonium hydroxide
Heat can be specifically 20-80 DEG C of heating, and the ammonia and water vapour for so that it is volatilized are brought into together with protective gas.
Further include to described before carrying out the charing process and ammonium hydroxide activation process to the carbon nanobelts presoma
Carbon nanobelts presoma carries out the processing steps such as washing and dusting.Wherein, before carrying out washing treatment is to remove the carbon nanobelts
Unreacted reactant and solvent residues on body are driven, therefore, as long as the case where not influencing the carbon nanobelts presoma
Under, any washing methods that can remove reactant and dissolvent residual is within the scope of disclosed herein, as in an embodiment,
The carbon nanobelts presoma is repeatedly washed, is filtered, until filtrate close to it is neutral until, then drying and processing.
Dusting processing is carried out to the carbon nanobelts presoma after washing, conventional method progress may be used, such as basis
The carbon nanobelts presoma is carried out smashing processing by the requirement of grain size.
In above-mentioned steps S03, sulphur simple substance can volatilize after heated, after can be deposited on the porous of the nitrogen oxygen codope
In the surface of carbon nanobelts and its porous structure, so that sulphur simple substance can be uniformly porous with the nitrogen oxygen codope
Carbon nanobelts are checked, to improve the chemical property of the porous carbon nanobelts lithium sulphur lithium sulfur battery anode material.
In one embodiment, the weight ratio of the porous carbon nanobelts and elemental sulfur that control the nitrogen oxygen codope is (3-8)：(4-8)；Another
In one embodiment, the temperature of heat treatment that is to say that it is 150-250 DEG C to control the temperature of the elemental sulfur volatilization, at this temperature
The time of heat treatment and sedimentation time should be sufficient.
In one embodiment, it is by the porous carbon nanobelts of the nitrogen oxygen codope and elemental sulfur in CS2In solution
It is fully ground after mixing, is placed in closed container, make sulphur volatilization well into hollow at high temperature such as 150-250 DEG C
In the hole of carbon nanometer micro ball.
Therefore, the preparation method of above-mentioned porous carbon nanobelts lithium sulfur battery anode material passes through to processing step and condition
Setting so that prepare porous carbon nanobelts lithium sulfur battery anode material have large specific surface area, good wetability and
The content of high elemental sulfur, and sulfur fixation performance is significantly improved, effectively inhibit the chemical properties such as " the shuttle effect " of polysulfide.Separately
Outside, preparation method technique of the present invention is relatively easy, and condition is easily-controllable, efficient, prepares porous carbon nanobelts lithium-sulphur cell positive electrode material
Expect that performance is stablized.
Based on porous carbon nanobelts lithium sulfur battery anode material preparation method described above, the embodiment of the present invention also provides
A kind of porous carbon nanobelts lithium sulfur battery anode material, specifically, the porous carbon nanobelts lithium sulfur battery anode material by
Porous carbon nanobelts lithium sulfur battery anode material preparation method described above prepares.Therefore, the porous carbon nanobelts
Lithium sulfur battery anode material on the one hand have porous structure, and porous structure can be random distribution aperture it is unequal more
Grade pore structure, such as containing micropore, mesoporous and macropore (according to IUPAC (International Union of Pure and
Applied Chemistry, the international chemical combined meeting of unadulterated application) classification, can be big according to aperture by the duct in carbon material
It is small to be divided into macropore (＞ 50nm), mesoporous (2-50nm) and micropore (＜ 2nm)) hierarchical porous structure, it is after testing, above-mentioned porous
Carbon nanobelts lithium sulfur battery anode material specific surface area is up to 3000m2/g；On the other hand, the porous carbon nanobelts lithium sulphur electricity
Pond positive electrode surface bond has abundant nitrogen-containing functional group and oxygen-containing functional group, with good wetability and high elemental sulfur
Content significantly improves sulfur fixation performance, effectively inhibits the chemical properties such as " the shuttle effect " of polysulfide.Just because of described porous
Carbon nanobelts lithium sulfur battery anode material has the design feature, therefore, electric with high rate capability and cyclical stability etc.
Chemical property.By measuring, the thickness of the porous carbon nanobelts lithium sulfur battery anode material is 10-30nm, width 50-
200nm, length are micron order, if length is some tens of pm.
On the other hand, based on lithium sulfur battery anode material and preparation method thereof described above, the embodiment of the present invention also carries
A kind of lithium-sulphur cell positive electrode is supplied.The lithium-sulphur cell positive electrode may include the necessary component of lithium-sulphur cell positive electrode, such as include collection
Fluid and the positive-active layer being incorporated on the collector.
Wherein, collector can be common positive current collector material, such as aluminium foil.
The positive-active layer may include sulphur positive electrode, conductive agent and binder.Wherein, sulphur positive electrode, conduction
Agent and weight of binder ratio can be with but not just for (60-90)：(5-20)：(5-20) is further (70-90)：(5-15)：
(5:20).The binder can with but not only select PVDF, the conductive agent can with but not only select acetylene black.The sulphur
Positive electrode is porous carbon nanobelts lithium sulfur battery anode material described above.Therefore, porous carbon nanobelts described above are based on
The characteristic of lithium sulfur battery anode material.The lithium-sulphur cell positive electrode has larger specific capacity, higher high rate performance and good
Cyclical stability.In one embodiment, the positive-active layer will contain the sulphur positive electrode, conductive agent and binder
The thickness that slurry coats on a current collector is 50-300 μm, is then formed through drying process (such as vacuum, 40-100 DEG C).
On the basis of the lithium-sulphur cell positive electrode, the embodiment of the present invention additionally provides a kind of lithium-sulfur cell.The lithium sulphur
Battery includes necessary component, such as including anode and cathode component, wherein the just extremely lithium-sulfur cell of the embodiment of the present invention
Anode.In this way, the lithium-sulfur cell specific capacity, higher high rate performance and good cyclical stability.
Now by taking specific porous carbon nanobelts lithium sulfur battery anode material and its preparation method and application as an example, to the present invention into
Row is further described.
1. porous carbon nanobelts lithium sulfur battery anode material and preparation method thereof embodiment
Embodiment 1
The present embodiment provides a kind of porous carbon nanobelts lithium sulfur battery anode materials and preparation method thereof.The porous carbon is received
Rice band lithium sulfur battery anode material preparation method includes the following steps：
S11：The dilute hydrochloric acid of 120g 10%, the formalin of 2.5g 37%, 1.65g hydroquinones are weighed, then three
30min is stirred until forming the solution of homogeneous transparent；
S12：The made solution of above-mentioned steps is poured into using polytetrafluoroethylene (PTFE) as in the hydrothermal reaction kettle of liner, by water heating kettle
Sealing is put into 180 DEG C of baking oven, reacts cooled to room temperature after 12h；
S13：Products therefrom in above-mentioned steps is filtered, and is washed with deionized 5 times, vacuum drying is subsequently placed in
In case, 60 DEG C of dryings are for 24 hours；
S14：By dry product (carbon nanobelts presoma) grind into powder, sealing collection is spare；
S15：It takes 1.5g carbon nanobelts to be put in corundum crucible, crucible is put in tube furnace, be 50ml/min with flow
Argon gas ammonia that the ammonium hydroxide (50 DEG C) of heating is decomposed discord vapor is passed through in tube furnace, be filled in tube furnace at this time
The mixed gas of argon gas, vapor and ammonia；
S16：Tube furnace is begun to warm up from room temperature, and the rate of heat addition is 5 DEG C/min, is heated to 950 DEG C of heat preservation 40min, then
It is cooled to room temperature the porous carbon nanobelts for obtaining nitrogen oxygen codope；
S17：4ml CS will be added after the porous carbon nanobelts of 160mg nitrogen oxygen codopes and the grinding uniformly of 240mg sulphur2Into one
Step grinding, until CS2Volatilization completely after mixture is placed in closed container, at 155 DEG C keep 12h under make sulphur volatilization be able into
It obtains loading the more of the nitrogen oxygen codope for having sulphur in the hole for entering the porous carbon nanobelts of nitrogen oxygen codope, after being cooled to room temperature
Hole carbon nanobelts, i.e., porous carbon nanobelts lithium sulfur battery anode material.
Embodiment 2
The present embodiment provides a kind of porous carbon nanobelts lithium sulfur battery anode materials and preparation method thereof.The porous carbon is received
Rice band lithium sulfur battery anode material preparation method includes the following steps：
S11：The dilute hydrochloric acid of 125g 10%, the formalin of 2.8g 37%, 1.5g hydroquinones are weighed, then three stirs
Mix 20min；
S12：The made solution of above-mentioned steps is poured into using polytetrafluoroethylene (PTFE) as in the hydrothermal reaction kettle of liner, by water heating kettle
Sealing is put into 150 DEG C of baking oven, reacts cooled to room temperature after 15h；
S13：Products therefrom in above-mentioned steps is filtered, and is washed with deionized 6 times, normal drying is subsequently placed in
In case, 80 DEG C of dry 15h；
S14：By dry product (carbon nanobelts presoma) grind into powder, sealing collection is spare；
S15：It takes 1.0g carbon nanobelts to be put in corundum crucible, crucible is put in tube furnace, be 80ml/min with flow
Argon gas ammonia that the ammonium hydroxide (40 DEG C) of heating is decomposed discord vapor is passed through in tube furnace, be filled in tube furnace at this time
The mixed gas of argon gas, vapor and ammonia；
S16：Tube furnace is begun to warm up from room temperature, and the rate of heat addition is 5 DEG C/min, is heated to 800 DEG C of heat preservation 90min, then
It is cooled to room temperature the porous carbon nanobelts for obtaining nitrogen oxygen codope；
S17：5ml CS will be added after the porous carbon nanobelts of 200mg nitrogen oxygen codopes and the grinding uniformly of 200mg sulphur2Into one
Step grinding, until CS2Volatilization completely after mixture is placed in closed container, at 160 DEG C keep 10h under make sulphur volatilization be able into
It obtains loading the more of the nitrogen oxygen codope for having sulphur in the hole for entering the porous carbon nanobelts of nitrogen oxygen codope, after being cooled to room temperature
Hole carbon nanobelts, i.e., porous carbon nanobelts lithium sulfur battery anode material.
Embodiment 3
The present embodiment provides a kind of porous carbon nanobelts lithium sulfur battery anode materials and preparation method thereof.The porous carbon is received
Rice band lithium sulfur battery anode material preparation method includes the following steps：
S11：The dilute hydrochloric acid of 100g 15%, the formalin of 2.0g 37%, 1.2g hydroquinones are weighed, then three stirs
Mix 60min；
S12：The made solution of above-mentioned steps is poured into using polytetrafluoroethylene (PTFE) as in the hydrothermal reaction kettle of liner, by water heating kettle
Sealing is put into 190 DEG C of baking oven, reacts cooled to room temperature after 8h；
S13：Products therefrom in above-mentioned steps is filtered, and is washed with deionized 5 times, normal drying is subsequently placed in
In case, 100 DEG C of dry 12h；
S14：By dry product (carbon nanobelts presoma) grind into powder, sealing collection is spare；
S15：It takes 1.2g carbon nanobelts to be put in corundum crucible, crucible is put in tube furnace, be 40ml/min with flow
Argon gas ammonia that the ammonium hydroxide (60 DEG C) of heating is decomposed discord vapor is passed through in tube furnace, be filled in tube furnace at this time
The mixed gas of argon gas, vapor and ammonia；
S16：Tube furnace is begun to warm up from room temperature, and the rate of heat addition is 10 DEG C/min, is heated to 900 DEG C of heat preservation 30min, then
It is cooled to room temperature the porous carbon nanobelts for obtaining nitrogen oxygen codope；
S17：3ml CS will be added after the porous carbon nanobelts of 150mg nitrogen oxygen codopes and the grinding uniformly of 250mg sulphur2Into one
Step grinding, until CS2Volatilization completely after mixture is placed in closed container, at 160 DEG C keep 10h under make sulphur volatilization be able into
It obtains loading the more of the nitrogen oxygen codope for having sulphur in the hole for entering the porous carbon nanobelts of nitrogen oxygen codope, after being cooled to room temperature
Hole carbon nanobelts, i.e., porous carbon nanobelts lithium sulfur battery anode material.
Embodiment 4
The present embodiment provides a kind of porous carbon nanobelts lithium sulfur battery anode materials and preparation method thereof.The porous carbon is received
Rice band lithium sulfur battery anode material preparation method includes the following steps：
S11：The dilute hydrochloric acid of 150g 8%, the formalin of 3.0g 37%, 2g hydroquinones are weighed, then three mixes
Uniform stirring 35min；
S12：The made solution of above-mentioned steps is poured into using polytetrafluoroethylene (PTFE) as in the hydrothermal reaction kettle of liner, by water heating kettle
Sealing is put into 170 DEG C of baking oven, reacts cooled to room temperature after 14h；
S13：Products therefrom in above-mentioned steps is filtered, and is washed with deionized 5 times, hollow drying is subsequently placed in
In case, 70 DEG C of dry 20h；
S14：By dry product (carbon nanobelts presoma) grind into powder, sealing collection is spare；
S15：It takes 1.0g carbon nanobelts to be put in corundum crucible, crucible is put in tube furnace, be 60ml/min with flow
Argon gas ammonia that the ammonium hydroxide (30 DEG C) of heating is decomposed discord vapor is passed through in tube furnace, be filled in tube furnace at this time
The mixed gas of argon gas, vapor and ammonia；
S16：Tube furnace is begun to warm up from room temperature, and the rate of heat addition is 4 DEG C/min, is heated to 850 DEG C of heat preservation 70min, then
It is cooled to room temperature the porous carbon nanobelts for obtaining nitrogen oxygen codope；
S17：2ml CS will be added after the porous carbon nanobelts of 100mg nitrogen oxygen codopes and the grinding uniformly of 120mg sulphur2Into one
Step grinding, until CS2Volatilization completely after mixture is placed in closed container, at 200 DEG C keep 8h under make sulphur volatilization be able into
The porous carbon nanobelts that load has the nitrogen oxygen codope of sulphur are obtained in the hole for entering carbon nanobelts, after being cooled to room temperature, i.e., it is more
Hole carbon nanobelts lithium sulfur battery anode material.
Embodiment 5
The present embodiment provides a kind of porous carbon nanobelts lithium sulfur battery anode materials and preparation method thereof.The porous carbon is received
Rice band lithium sulfur battery anode material preparation method includes the following steps：
S11：The dilute hydrochloric acid of 80g 15%, the formalin of 2.4g 37%, 1.2g hydroquinones are weighed, then three stirs
Mix 30min；
S12：The made solution of above-mentioned steps is poured into using polytetrafluoroethylene (PTFE) as in the hydrothermal reaction kettle of liner, by water heating kettle
Sealing is put into 175 DEG C of baking oven, reacts cooled to room temperature after 10h；
S13：Products therefrom in above-mentioned steps is filtered, and is washed with deionized 5 times, normal drying is subsequently placed in
In case, 120 DEG C of dry 12h；
S14：By dry product (carbon nanobelts presoma) grind into powder, sealing collection is spare；
S15：It takes 2.0g carbon nanobelts to be put in corundum crucible, crucible is put in tube furnace, be 30ml/min with flow
Argon gas ammonia that the ammonium hydroxide (55 DEG C) of heating is decomposed discord vapor is passed through in tube furnace, be filled in tube furnace at this time
The mixed gas of argon gas, vapor and ammonia；
S16：Tube furnace is begun to warm up from room temperature, and the rate of heat addition is 6 DEG C/min, is heated to 750 DEG C of heat preservation 120min, then
It is cooled to room temperature the porous carbon nanobelts for obtaining nitrogen oxygen codope；
S17：2ml CS will be added after the porous carbon nanobelts of 100mg nitrogen oxygen codopes and the grinding uniformly of 80mg sulphur2Into one
Step grinding, until CS2Volatilization completely after mixture is placed in closed container, at 165 DEG C keep 12h under make sulphur volatilization be able into
It obtains loading the more of the nitrogen oxygen codope for having sulphur in the hole for entering the porous carbon nanobelts of nitrogen oxygen codope, after being cooled to room temperature
Hole carbon nanobelts, i.e., porous carbon nanobelts lithium sulfur battery anode material.
Further by the porous carbon nanobelts of the present embodiment 1-5 carbon nanobelts presomas prepared and nitrogen oxygen codope and
Porous carbon nanobelts lithium sulfur battery anode material is scanned Electronic Speculum respectively, wherein the carbon nanobelts presoma that embodiment 1 provides
Scanning electron microscopic picture as shown in Figure 1, the scanning electron microscope of the porous carbon nanobelts of nitrogen oxygen codope is as shown in Figure 2.By Fig. 1 and 2
It is found that the porous carbon nanobelts of the carbon nanobelts presoma and nitrogen oxygen codope are banded structure, and the ruler of banded structure
Very little such as length and span are nanoscale, and size distribution is uniform.Porous carbon nanobelts lithium-sulfur cell through being prepared to embodiment 1
Positive electrode is scanned electron-microscope scanning, learns the porous carbon nanobelts of its form and size and nitrogen oxygen codope in embodiment 1
It is essentially identical.The porous carbon nanobelts and porous carbon nanobelts of carbon nanobelts presoma and nitrogen oxygen codope in embodiment 2-5
It is approximate with embodiment 1 that lithium sulfur battery anode material is scanned electron microscopic picture respectively.
The porous carbon nanobelts of nitrogen oxygen codope prepared by embodiment 1-5 are further subjected to physical adsorption property and aperture
Distribution and X-ray photoelectron spectroscopic analysis, wherein the physical absorption of the porous carbon nanobelts of 1 nitrogen oxygen codope of embodiment is bent
Line (BET) as shown in figure 3, pore size distribution curve as shown in figure 4, X-ray photoelectron spectroscopic analysis image is as shown in Figure 5.By Fig. 3
It is found that the nitrogen adsorption desorption curve of the porous carbon nanobelts of the nitrogen oxygen codope is typical I/IV types adsorption curve, all it is
(the P/P under low relative pressure0<0.05)N2Adsorbance, which first steeply rises, is then rapidly reached balance, this illustrates all nitrogen oxygen
The porous carbon nanobelts of codope include that there is a large amount of micropore (＜ 2nm) knots for porous carbon nanobelts lithium sulfur battery anode material
Structure, in P/P0Ranging from 0.9~1 region, the porous carbon nanobelts of all nitrogen oxygen codopes, porous carbon nanobelts lithium sulphur electricity
The desorption curve of pond positive electrode all obviously lags behind adsorption curve, thus forms a lag winding, this shows that nitrogen oxygen is total
There is also numerous mesoporous (2-50nm) inside the porous carbon nanobelts and porous carbon nanobelts lithium sulfur battery anode material of doping
With macropore (＞ 50nm).As shown in Figure 4, the porous carbon nanobelts of the nitrogen oxygen codope have point in micropore, mesoporous and macropore
Cloth is with hierarchical porous structure；As shown in Figure 5, the porous carbon nanobelts of the nitrogen oxygen codope contain C, N, O element, therefore,
It contains hydrophilic radical nitrogen groups and oxygen groups.
The physical adsorption property test result that the porous carbon nanobelts of embodiment 2-5 nitrogen oxygen codopes carry out respectively and implementation
Example 1 is similar.
2. electrode of super capacitor and ultracapacitor embodiment
Embodiment 6
The present embodiment provides a kind of electrode of super capacitor and ultracapacitors.
The present embodiment ultracapacitor includes electrode and other necessary parts, wherein the electrode is made as follows
It is standby：
There are the nitrogen-doped carbon nanobelt, PVDF powder and acetylene black of sulphur there are 2ml N-Methyl pyrrolidones load
(NMP) coating that 200 μ m-thicks are uniformly then applied on aluminium foil is ground in mortar.Wherein load has the nitrogen-doped carbon of sulphur to receive
Rice band：PVDF:Acetylene black is with weight ratio for 8:1:1；The aluminium foil for being then coated with electrode material is placed in vacuum drying chamber, 60 DEG C
Then hollow dry 12h uses sheet-punching machine, be electrode slice by the aluminium foil punching containing electrode material.
Embodiment 7
The present embodiment provides a kind of electrode of super capacitor and ultracapacitors.
The present embodiment ultracapacitor includes electrode and its other necessary parts, wherein the electrode is as follows
It prepares：
There are the nitrogen-doped carbon nanobelt, PVDF powder and acetylene black of sulphur there are 2ml N-Methyl pyrrolidones load
(NMP) coating that 100 μ m-thicks are uniformly then applied on aluminium foil is ground in mortar.Wherein load has the nitrogen-doped carbon of sulphur to receive
Rice band：PVDF:Acetylene black is with weight ratio for 85:7:8；Then the aluminium foil for being coated with electrode material is placed in vacuum drying chamber,
Then 50 DEG C of hollow dry 15h use sheet-punching machine, be electrode slice by the aluminium foil punching containing electrode material.
7 ultracapacitor of the present embodiment is subjected to related electrochemical property test, test result and super electricity in embodiment 6
Container performance is close.
Embodiment 8
The present embodiment provides a kind of electrode of super capacitor and ultracapacitors.
The present embodiment ultracapacitor includes electrode and its other necessary parts, wherein the electrode is as follows
It prepares：
There are the nitrogen-doped carbon nanobelt, PVDF powder and acetylene black of sulphur there are 1.5ml N-Methyl pyrrolidones load
(NMP) coating that 50 μ m-thicks are uniformly then applied on aluminium foil is ground in mortar.Wherein load has the nitrogen-doped carbon of sulphur to receive
Rice band：PVDF:Acetylene black is with weight ratio for 80:8:12；Then the aluminium foil for being coated with electrode material is placed in vacuum drying chamber,
Then 70 DEG C of hollow dry 10h use sheet-punching machine, be electrode slice by the aluminium foil punching containing electrode material.
8 ultracapacitor of the present embodiment is subjected to related electrochemical property test, test result and super electricity in embodiment 6
Container performance is close.
Embodiment 9
The present embodiment provides a kind of electrode of super capacitor and ultracapacitors.
The present embodiment ultracapacitor includes electrode and its other necessary parts, wherein the electrode is as follows
It prepares：
There are the nitrogen-doped carbon nanobelt, PVDF powder and acetylene black of sulphur there are 2ml N-Methyl pyrrolidones load
(NMP) coating that 150 μ m-thicks are uniformly then applied on aluminium foil is ground in mortar.Wherein load has the nitrogen-doped carbon of sulphur to receive
Rice band：PVDF:Acetylene black is with weight ratio for 78:11:11；Then the aluminium foil for being coated with electrode material is placed in vacuum drying chamber
In, then 55 DEG C of hollow dry 15h use sheet-punching machine, be electrode slice by the aluminium foil punching containing electrode material.
9 ultracapacitor of the present embodiment is subjected to related electrochemical property test, test result and super electricity in embodiment 6
Container performance is close.
Embodiment 10
The present embodiment provides a kind of electrode of super capacitor and ultracapacitors.
The present embodiment ultracapacitor includes electrode and its other necessary parts, wherein the electrode is as follows
It prepares：
There are the nitrogen-doped carbon nanobelt, PVDF powder and acetylene black of sulphur there are 2ml N-Methyl pyrrolidones load
(NMP) coating that 100 μ m-thicks are uniformly then applied on aluminium foil is ground in mortar.Wherein load has the nitrogen-doped carbon of sulphur to receive
Rice band：PVDF:Acetylene black is with weight ratio for 75:10:15；Then the aluminium foil for being coated with electrode material is placed in vacuum drying chamber
In, then 80 DEG C of hollow dry 10h use sheet-punching machine, be electrode slice by the aluminium foil punching containing electrode material.
10 ultracapacitor of the present embodiment is subjected to related electrochemical property test, test result with it is super in embodiment 6
Capacitor performance is close.
The present embodiment 6-10 is provided to the lithium-sulfur cell provided in lithium-sulfur cell and comparative example and carries out related electrochemistry respectively
Performance test, assay method and result are as follows：
Assay method：It measures and contains positive material under the voltage capacity curve and 1C multiplying powers of the positive electrode under 0.1C multiplying powers
The lithium-sulfur cell cycle performance of material.
Measurement result：The lithium-sulfur cell that embodiment 6 provides first capacity of putting of electrode under 0.1C multiplying powers can reach
1361mA·h·g- 1, the first capacity of putting of electrode can reach 770mAhg under 1C multiplying powers- 1, and pass through under 1C multiplying powers
300 charge and discharge cycles can still keep 475mAhg- 1Capacity.
Due to prepared lithium sulfur battery anode material, pore volume is big, nitrogen content is high has hierarchical porous structure, therefore has
Higher capacity and good high rate performance, and can effectively inhibit the shuttle in charge and discharge process to imitate in charge and discharge process
It answers, there is higher appearance for the lithium sulfur battery anode material compared to Publication No. CN106981649A and CN106654231
Amount and excellent high rate performance and good cyclical stability.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all essences in the present invention
All any modification, equivalent and improvement etc., should all be included in the protection scope of the present invention made by within refreshing and principle.
Claims (10)
1. a kind of preparation method of porous carbon nanobelts lithium sulfur battery anode material, which is characterized in that include the following steps：
Formaldehyde, hydroquinone are subjected to hydro-thermal reaction in an acidic solution, obtain carbon nanobelts presoma；
By the carbon nanobelts presoma through charing process and ammonium hydroxide activation process, the porous carbon nanometer of nitrogen oxygen codope is obtained
Band；
After the porous carbon nanobelts and elemental sulfur are carried out mixture, it is heat-treated in closed environment so that the list
Matter sulphur volatilizees and is deposited in the porous carbon nanobelts.
2. preparation method according to claim 1, which is characterized in that the temperature of the hydro-thermal reaction is 120-200 DEG C, instead
It is 8-16h between seasonable.
3. preparation method according to claim 1 or 2, which is characterized in that the quality of the formaldehyde and the hydroquinone
Than for (1-5)：(1-4)；And/or
The mass ratio of the acid solution and the hydroquinone is (50-150)：(1-4)；And/or
Described in acid solution is the dilute hydrochloric acid that mass concentration is 5%-20%.
4. preparation method according to claim 1 or 2, it is characterised in that：The charing process and ammonium hydroxide activation process
Method is as follows：
In protective atmosphere, the carbon nanobelts presoma is heat-treated at 700-1000 DEG C；And the protectiveness
Atmosphere contains the mixed gas of the ammonia and vapor that are thermally decomposed to generate by ammonium hydroxide.
5. preparation method according to claim 4, it is characterised in that：The time of the heat treatment is 20-120min；With/
Or
It is that 2-10 DEG C/min is warming up to 700-1000 DEG C that the heat treatment temperature, which is with heating rate,.
6. according to claim 1,2 and 5 any one of them preparation methods, it is characterised in that：The porous carbon nanobelts and list
The weight ratio of matter sulphur is (3-8)：(4-8)；And/or
The temperature of the elemental sulfur volatilization is 150-250 DEG C.
7. a kind of porous carbon nanobelts lithium sulfur battery anode material, which is characterized in that the porous carbon nanobelts lithium-sulfur cell is just
Pole material is prepared by claim 1-6 any one of them preparation methods.
8. porous carbon nanobelts lithium sulfur battery anode material according to claim 7, which is characterized in that the porous carbon is received
Thickness of the rice with lithium sulfur battery anode material is 10-30nm, and width 50-200nm, length is micron order；And/or
The porous carbon nanobelts lithium sulfur battery anode material contains porous structure.
9. a kind of lithium-sulphur cell positive electrode, including collector and the positive-active layer that is incorporated on the collector, which is characterized in that
The positive-active layer includes sulphur positive electrode, conductive agent and binder, wherein the sulphur positive electrode is claim 7 or 8
The lithium sulphur positive electrode.
10. a kind of lithium-sulfur cell, including anode and cathode, which is characterized in that the lithium sulphur electricity just extremely described in claim 9
Pond anode.
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| CN110931744A (en) * | 2019-11-29 | 2020-03-27 | 深圳技术大学 | Silicon-carbon negative electrode material and preparation method thereof |
| CN111180681A (en) * | 2018-11-12 | 2020-05-19 | 天津师范大学 | High-load lithium-sulfur positive electrode material and preparation method and application thereof |
| CN112018310A (en) * | 2020-06-19 | 2020-12-01 | 大连理工大学 | Resin-based carbon nanofiber membrane applied to lithium-sulfur battery interlayer and preparation method thereof |
| CN112259903A (en) * | 2020-09-23 | 2021-01-22 | 华南师范大学 | Nitrogen-doped porous carbon loaded metal cobalt material and preparation method and application thereof |
| CN114335524A (en) * | 2022-03-15 | 2022-04-12 | 中国长江三峡集团有限公司 | Heteroatom-doped porous carbon nanobelt material and preparation method and application thereof |
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| CN111180681A (en) * | 2018-11-12 | 2020-05-19 | 天津师范大学 | High-load lithium-sulfur positive electrode material and preparation method and application thereof |
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