CN107732184A - Lithium-sulfur battery composite anode material of one-dimensional N doping double-layer carbon shell/sulphur and preparation method thereof - Google Patents
Lithium-sulfur battery composite anode material of one-dimensional N doping double-layer carbon shell/sulphur and preparation method thereof Download PDFInfo
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Abstract
One-dimensional N doping double-layer carbon shell/sulphur composite positive pole and preparation method thereof, material are the elongated double-layer carbon housing of nitrogen-doped carbon material system, and nanoparticle elemental sulfur is dispersed between carbon shell；Preparation method is using double-layer carbon shell as solid sulphur presoma, elemental sulfur is evenly dispersed in the form of nanoparticle in double-layer carbon shell through vacuum fusion salt method.The present invention controls sulphur particle size and content by the unidimensional scale of carbon shell, improves the utilization rate of sulphur；Increase the contact area of sulphur and electrolyte by double-layer carbon shell, improve the utilization rate of sulphur；The conductance of sulphur is improved by the graphitized carbon of N doping；The chemical coordination of the seal of carbon shell, double-decker and nitrogen sulphur is acted on to improve the loss of polysulfide, improves the cycle performance of electrode material.Simple operations convenience and excellent material performance are prepared, specific discharge capacity is big, and big multiplying power and long circulating performance are good, has broad prospect of application in fields such as mobile communication, portable electric appts, energy storage device, unmanned plane and electric automobiles.
Description
Technical field
The present invention relates to cell positive material technical field, and in particular to a kind of height ratio capacity, long circulation life, high magnification
The lithium-sulfur battery composite anode material of one-dimensional N doping double-layer carbon shell/sulphur of performance.The invention further relates to the preparation of the material
Method.
Background technology
It is right with developing rapidly for the related industries such as mobile communication, portable electric appts, electric automobile and energy storage device
The performance of battery, particularly specific capacity, energy density, cycle life and high rate performance etc., it is proposed that higher and higher requirement.Cause
This, exploitation is with high-performance, low cost and environmentally friendly new type lithium ion secondary cell with very important strategic importance.
Performance and price of positive electrode etc. are to restrict lithium ion battery further to high-energy-density, long-life and low cost to develop
Bottleneck.Such as existing LiFePO4、LiMn2O4And the positive electrode such as ternary material, due to being limited by its relatively low theoretical capacity,
Its specific capacity, the room for promotion of energy density are very limited.Therefore, high-energy-density, long circulation life and low cost is new
The research and development of anode material for lithium-ion batteries are the inexorable trends of lithium ion battery technology development.Elemental sulfur has higher
Theoretical specific capacity (1675mAh/g) and higher theory are than energy (2600Wh/kg), and rich reserves, cheap, environment
The advantages that friendly, it is expected to turn into the excellent positive electrode of energy-density lithium ion battery.However, the poorly conductive of elemental sulfur in itself
(under 25 degrees Celsius of normal temperature, conductance is only 5 × 10-30S/cm the more vulcanizations), and in charge and discharge process formed with lithium ion
Thing is soluble in organic electrolyte, result in using elemental sulfur as lithium-sulfur cell poor circulation, the specific capacity that positive pole is constructed it is low, times
The shortcomings of rate poor performance, so as to constrain the further marketization of lithium-sulfur cell.At present, existing many research works both domestic and external
Person improves the chemical property of sulfur electrode using various methods, is answered for example with carbon material and oxide material with improving sulphur positive pole
The electric conductivity and cycle performance of condensation material.Wherein, carbon material includes the activated carbon of various pore structures, carbon pipe, carbon fiber, graphite
Alkene, graphene oxide etc.；Oxide material includes cobalt oxide, titanium oxide, silica, manganese oxide etc..These carbon materials and oxidation
The application of thing material so that some aspect performances of sulphur anode composite material are improved, such as specific capacity, high rate performance,
Cycle performance etc..But the lithium-sulfur cell research of big multiplying power is also fewer, due to electric automobile and unmanned aerial vehicle etc. start with
Acceleration needs moment relatively high power, and this is current lithium-sulfur cell problem encountered, it is desirable to is accounted in the energy field in future
One seat, it is also necessary to research and develop the lithium sulfur battery anode material of big multiplying power, height ratio capacity and long circulating performance.
The content of the invention
First technical problem to be solved by this invention, just it is to provide a kind of lithium of one-dimensional N doping double-layer carbon shell/sulphur
Sulphur battery composite anode material.
Second technical problem to be solved by this invention, is just to provide a kind of preparation method of above-mentioned material.
Using the material obtained by the preparation method of the present invention, structure is novel, excellent performance and is expected to heavy industrialization
Produce the lithium-sulfur cell of height ratio capacity, high rate capability and long circulation life.
Solve above-mentioned first technical problem, the present invention adopts the following technical scheme that：
A kind of lithium-sulfur cell composite anode material of one-dimensional N doping double-layer carbon shell/sulphur, it is characterized in that：For with N doping
Elongated double-layer carbon housing made of carbon material, the elemental sulfur of nanop articulate form is dispersed between double-layer carbon shell.
Remarks：In this Material Field, one-dimensional finger has size in two dimensions to be in Nano grade, such as nano wire, nanometer
Pipe, nanobelt shape structure；Two dimension：Size is in Nano grade, such as nano-lamellar structure in one dimension.
The present invention is using porous one-dimensional N doping double-layer carbon shell as solid sulphur presoma, makes elemental sulfur by vacuum fusion salt method
It is evenly dispersed in the form of nanoparticle in carbon shell bilayer, sulphur is controlled by the unidimensional scale of carbon shell and the thickness of bilayer
The size and sulfur content of particle, improve the utilization rate of sulphur；The conductance of sulphur is improved by the graphitized carbon of N doping；Carbon shell
The coordination of seal and nitrogen sulphur improves the loss of more lithium sulfides, improves the cycle performance of material, so as to realize Fabrication of High Specific Capacitance
Measure, the preparation of the positive electrode of big multiplying power long circulation life.
Solve above-mentioned second technical problem, the present invention adopts the following technical scheme that：
A kind of method for preparing anode material as described above, it is characterized in that comprising the following steps：
(1) by FeCl3And NH4H2PO4According to conventional mol ratio 20:1~100:It is put into after 1 mixing in hydrothermal reaction kettle,
Heated 8~30 hours under the conditions of 200~250 degree, be cooled to conventional filtration after room temperature and clean, obtain one-dimensional there is hollow structure
Fe2O3The presoma of rod；The Fe that will be obtained2O3Presoma is distributed in the polymer monomer aqueous solution and stirred 2~4 hours, conventional
Filtering cleaning, vacuum drying obtain one-dimensional PDA@Fe2O3 composites；(@refers to cladding)
(2) resulting composite is put into and be connected with the tube furnace of protection gas, high temperature cabonization 1~4 hour, temperature
900~1200 DEG C, then products therefrom be put into the aqueous hydrochloric acid solution of 0.1 mol/L and etch 4~6 hours, routinely cleaned
Filter, obtains one-dimensional N doping double-layer carbon shell after vacuum drying；
(3) by business sulphur powder and one-dimensional N doping double-layer carbon shell according to 1:1~3:1 mass ratio mixing, is then placed in
In closed container, vacuum is evacuated to as after 100~500Pa, 180 are risen to from room temperature with 2 degrees/min of heating rate~
300 degree, 10~20 hours are incubated, is naturally cooling to 155 degree~160 degree, is incubated 10~20 hours, then with 20 degrees/min~50
Degree/min rate of temperature fall be cooled to room temperature, you can obtain one-dimensional N doping double-layer carbon shell/sulphur composite.
Preferably, the concentration of the polymer monomer aqueous solution described in step (1) is 0.5g~3g/L, and polymer monomer is salt
Sour dopamine.
Preferably, the protective gas described in step (2) is nitrogen, argon hydrogen gaseous mixture (Ar:H2=3:1~9:Or ammonia 1)
Argon gas gaseous mixture (Ar:NH3=1:1~2:1) one kind in, the flow velocity of gas are the ml/min of 50 ml/mins~300.
Beneficial effect：Compared with prior art, the advantage of the invention is that：(1) preparation process is easily operated, with more
The one-dimensional N doping double-layer carbon shell in hole is presoma, and one-dimensional N doping is realized by physical chemistry effect caused by vacuum fusion method
Double-layer carbon shell/magister of sulfur；(2) by the thickness and length of one-dimensional N doping double-layer carbon shell come control the size of the particulate of sulphur and
Sulfur content, improve the utilization rate and specific capacity of sulphur；Inhaled by the seal of carbon shell and the chemistry of the nitrogen and more lithium sulfides that are adulterated
Attached effect, the loss of caused more lithium sulfides in charge and discharge process is more effectively prevented, be advantageous to improve the coulomb effect of battery
Rate and the cycle life for improving battery；(3) nitrogen-doped carbon microballoon has conductance more more preferable than common carbon material, is favorably improved
The high rate performance of battery；(4) method is simple to operation, is adapted to large-scale industrial production.
Brief description of the drawings
Fig. 1 is transmission electron microscope (TEM) photo of the one-dimensional N doping double-layer carbon shell in the embodiment of the present invention；
Fig. 2 is the TEM transmission electron microscopes (TEM) of one-dimensional N doping double-layer carbon shell/sulphur in the embodiment of the present invention one
Photo；
Fig. 3 is the 0.5C of one-dimensional N doping double-layer carbon shell/sulphur in the embodiment of the present invention one cycle performance figure；
Fig. 4 is the 1C of one-dimensional N doping double-layer carbon shell/sulphur in the embodiment of the present invention one cycle performance figure；
Fig. 5 is the lithium-sulfur cell composite anode material longitudinal sectional view of one-dimensional N doping double-layer carbon shell/sulphur of the present invention；
Fig. 6 is Fig. 4 transverse sectional view.
Reference refers in figure：1- outer layer nitrogen-doped carbon shells, 2- internal layer nitrogen-doped carbon shells, the list of 3- nanop articulate forms
Matter sulphur.
Embodiment
The present invention is further described in detail below by the drawings and specific embodiments.
Structure such as Fig. 5 and Fig. 6, photo are as shown in figure 1, the lithium-sulfur cell of one-dimensional N doping double-layer carbon shell/sulphur of the present invention
Composite anode material embodiment, it is with double-layer carbon housing elongated made of nitrogen-doped carbon material, outer layer carbon shell 1 and internal layer carbon
The elemental sulfur 3 of nanop articulate form is dispersed between shell 2.
Method for preparing anode material as described above have following examples.
Embodiment one
The first step：By FeCl3And NH4H2PO4According to mol ratio 28:It is put into after 1 mixing in hydrothermal reaction kettle, at 240 degree
Under the conditions of heat 20 hours, be cooled to after room temperature and filter cleaning, obtain hollow Fe2O3The presoma of rod；The Fe that will be obtained2O3
Presoma is distributed in the aqueous dopamine solution of 0.5g concentration and stirred 2 hours, and filtering cleaning, vacuum drying obtains PDA@Fe2O3
Composite；
Second step：Resulting composite is put into and is connected with argon gas ammonia gas mixture (Ar:NH3=1:1) tubular type
In stove, the flow velocity of gas is 50 ml/mins, high temperature cabonization 1 hour, 1000 DEG C of temperature, and then products therefrom is put into concentration and is
Etched 4 hours in 0.1 mole every liter of aqueous hydrochloric acid solution, be dried in vacuo after cleaning filtering, obtain one-dimensional N doping double-layer carbon
Shell.
3rd step：By business sulphur powder and one-dimensional N doping double-layer carbon shell according to 3:1 part by weight mixing, is then placed in
In closed container, after vacuumizing, vacuum 500Pa, temperature rises to 300 degree with 2 degrees/min of speed, is incubated 12 hours,
Then 155 degree are cooled to, 12 hours is incubated, is rapidly cooled to room temperature and can obtain one-dimensional N doping double-layer carbon shell/sulphur composite wood
Material, cooldown rate are 50 degrees/min.
The preparation of lithium-sulfur cell：One-dimensional N doping double-layer carbon shell/sulphur composite, carbon black and Kynoar (PVDF)
It is 8 according to mass ratio:1:1 proportioning is mixed, then appropriate 1-METHYLPYRROLIDONE (NMP) is added dropwise, and then carries out ball milling
The revolution of batch mixing, wherein ball mill is 200 revs/min, and Ball-milling Time is 6 hours.The good slurry of ball milling is uniformly applied to aluminium
Above paper tinsel, vacuum drying treatment (drying temperature is 60 degrees Celsius, and drying time is 4 hours) is carried out, as positive electrode.Negative pole
Material is metal lithium sheet, and polypropylene porous film is battery diaphragm, and electrolyte is to contain 1% LiNO3Concentration be 1 mol/L
LiTFSI DOL+DME (volume ratios 1:1).After button cell assembling is completed in the glove box of ar gas environment, in charge and discharge
Battery performance test is carried out on electric instrument.The voltage range of battery testing is 1.5V~2.8V.
Embodiment two
The first step：It is other identical with embodiment one in addition to being to heat 30 hours under the conditions of 220 degree；
Second step：Resulting composite is put into the tube furnace for being connected with nitrogen, the flow velocity of gas is 300 millis
Liter/min, high temperature cabonization 2 hours, 1000 DEG C of temperature, then products therefrom be put into concentration be 0.1 mole every liter hydrochloric acid it is water-soluble
Etched 4 hours in liquid, be dried in vacuo after cleaning filtering, obtain one-dimensional N doping double-layer carbon shell.
3rd step：By business sulphur powder and one-dimensional N doping double-layer carbon shell according to 2:1 part by weight mixing, is then placed in
In closed container, vacuum is evacuated to after 300Pa, to rise to 200 degree with 2 degrees/min of heating rate, insulation 12 is small
When, then it is cooled to 160 degree, is incubated 12 hours, being rapidly cooled to room temperature, to can obtain one-dimensional N doping double-layer carbon shell/sulphur compound
Material, cooldown rate are 30 degrees/min.
The preparation of lithium-sulfur cell is identical with embodiment one.
Embodiment three
The first step：It is identical with embodiment one in addition to being to heat 10 hours under the conditions of 250 degree；
Second step：Resulting composite is put into and is connected with the tube furnace of protection gas, high temperature cabonization 2 hours, temperature
1200 DEG C are spent, then products therefrom is put into the hydrochloric acid solution of appropriate concentration and etched 4 hours, is dried in vacuo, obtains after cleaning filtering
To one-dimensional N doping double-layer carbon shell.
3rd step：By business sulphur powder and one-dimensional N doping double-layer carbon shell according to 3:1 ratio mixing, is then placed in closed
In container, after vacuumizing, vacuum 100Pa, temperature slowly rises to 250 degree with 2 degrees/min of speed, is incubated 20 hours,
Then 155 degree are cooled to, 10 hours is incubated, is rapidly cooled to room temperature and can obtain one-dimensional N doping double-layer carbon shell/sulphur composite wood
Material, cooldown rate are 50 degrees/min.
The preparation of lithium-sulfur cell is identical with embodiment one.
Example IV
(1) by FeCl3And NH4H2PO4By normal mol ratio 20:It is put into after 1 ratio mixing in hydrothermal reaction kettle, at 200 degree
Under the conditions of heat 8 hours, be cooled to conventional filtration after room temperature and clean, obtain the one-dimensional Fe with hollow structure2O3The forerunner of rod
Body；The Fe that will be obtained2O3Presoma is distributed in the polymer monomer aqueous solution and stirred 2 hours, and filtering cleaning, vacuum drying obtains
One-dimensional PDA@Fe2O3 composites；The concentration of the described polymer monomer aqueous solution is 0.5g/L, and polymer monomer is hydrochloric acid
Dopamine；
(2) resulting composite is put into and is connected with argon hydrogen gaseous mixture (Ar:H2=3:1) in tube furnace, gas
Flow velocity be 50 ml/mins, high temperature cabonization 1 hour, 900 DEG C of temperature, then products therefrom be put into concentration as 0.1 mole every liter
The water-soluble middle etching of hydrochloric acid 4 hours, conventional vacuum is dried after conventional cleaning filtering, obtains one-dimensional N doping double-layer carbon shell；2
(3) by business sulphur powder and one-dimensional N doping double-layer carbon shell according to 1:1 ratio mixing, is then placed in closed container
It is interior, vacuum is evacuated to after 100Pa, to rise to 180 degree with 2 degrees/min of heating rate, being incubated 10 hours, be cooled to
155 degree, 10 hours are incubated, room temperature is cooled to 20 degrees/min of rate of temperature fall and can obtain one-dimensional N doping double-layer carbon shell/sulphur
Composite.
Embodiment five
(1) by FeCl3And NH4H2PO4According to 100:It is put into after 1 ratio mixing in hydrothermal reaction kettle, in 250 degree of conditions
Lower insulation is cooled to room temperature after 20 hours, then is cleaned through conventional filtration, obtains the one-dimensional Fe with hollow structure2O3Before rod
Drive body；The Fe that will be obtained2O3Presoma is distributed in the polymer monomer aqueous solution and stirred 4 hours, and conventional filtration cleaning, vacuum is done
One-dimensional PDA@Fe2O3 composites are obtained after dry；The concentration of the described polymer monomer aqueous solution is 3g/L, polymer monomer
For Dopamine hydrochloride；
(2) resulting composite is put into the tube furnace for being connected with nitrogen, the flow velocity of gas is 300 ml/mins
Clock, high temperature cabonization 4 hours, 1200 DEG C of temperature, then products therefrom be put into the hydrochloric acid solution of 0.1 mol/L and etch 6 hours,
Conventional cleaning filtering, obtains one-dimensional N doping double-layer carbon shell after vacuum drying；
(3) by business sulphur powder and one-dimensional N doping double-layer carbon shell according to 3:1 ratio mixing, is then placed in closed container
It is interior, vacuum is evacuated to after 500Pa, to make the heating rate of 2 degrees/min of temperature rise to 250 degree, is incubated 20 hours, drop
Temperature is incubated 20 hours to 160 degree, and being quickly cooled to room temperature with 50 degrees/min of rate of temperature fall can obtain one-dimensional N doping pair
Layer carbon shell/sulphur composite.
Testing result
Porous nitrogen-doped carbon microballoon and nitrogen-doped carbon the microsphere/sulfur composite wood prepared to above-described embodiment one by the present invention
Material has carried out TEM sign and electrochemical property test.It was found from Fig. 1 testing result, the length of the carbon shell of one-dimensional hollow is
340 nanometers, the outside dimension of shell is 190 nanometers, and the internal diameter of double shells is 80 nanometers.In addition, as shown in Figure 2, it can be seen that receive
Rice sulphur is circulated into a latitude N doping double-layer carbon shell completely, forms latitude N doping double-layer carbon shell parcel sulfur particle.Such as Fig. 3 institutes
Show, a latitude N doping double shells carbon/sulphur composite as cell positive material under 25 degrees Celsius of normal temperature, in 0.5C (1C=
Under discharge-rate 1675mA/g), initial discharge specific capacity is 1196mAh/g, and the specific discharge capacity after the circle of circulation 200 is
998mAh/g, the average capacity attenuation rate often enclosed are 0.082%；As shown in figure 4, in 1C (1C=1675mA/g) electric discharge times
Under rate, initial discharge specific capacity is 1089mAh/g, the specific discharge capacity after the circle of circulation 320 is 856mAh/g, average often to enclose
Capacity attenuation rate is 0.066%, and so high specific capacity and cycle performance have benefited from the double-deck knot of a latitude under the conditions of big multiplying power
Structure, the holding of the nanoscale of sulphur under the high conductivity of graphited nitrogen-doped carbon, and a latitude structure.Double-decker adds sulphur
With the contact area of electrolyte, the specific discharge capacity of battery is improved, the holding of the nanoscale of sulphur is also beneficial to high electric discharge
Specific capacity；The superior electrical conductivity of graphitization nitrogen-doped carbon is advantageous to improve the high rate performance and specific capacity of battery, so the application
In a latitude N doping double-layer carbon shell/sulphur composite there is so high specific discharge capacity and excellent under the conditions of 1C big multiplying power
Different cycle performance.
The method of the present invention is exactly to prepare Fe by masterplate method first2O3Hollow nanometer rods and nitrogenous monomer dopamine
(PDA) polymerisation obtains one-dimensional PDA@Fe2O3Presoma, secondly by obtaining one-dimensional N doping after high temperature cabonization and etching
Double-layer carbon shell, one-dimensional N doping double-layer carbon shell/sulphur composite positive pole is then prepared by vacuum fusion salt method.
By the polymerisation of nitrogenous polymer monomer dopamine, the hollow Fe prepared is completely coated on2O3Rod
Surfaces externally and internally, pass through different-diameter and the hollow Fe of length2O3Rod masterplate prepares various sizes of double-layer carbon shell；Pass through reagent
Concentration and the cladding time control the thickness of polymer film, it is by the protection to sulphur and the internal diameter and double shells of double-layer carbon carbon
Distance there is decisive action, so as to can also influence the content of sulphur, and the coulombic efficiency and cycle life of electrode；Pass through pyrocarbon
Change and nanometer Fe2O3Catalytic action to carbon adjusts the electric conductivity of the degree of graphitization of PDA polymeric materials and material, has
Beneficial to utilization rate, specific discharge capacity and the high rate performance for improving sulphur simple substance.
One-dimensional N doping double-layer carbon shell structure can significantly increase the performance of battery：One-dimentional structure can preferably control sulphur
The size of particulate, the secondary agglomeration after sulphur simple substance discharge and recharge is prevented, be advantageous to improve the service efficiency of sulphur；One-dimentional structure can increase
Add the contact area of sulphur and electrolyte, improve the specific capacity of battery；Double-decker, add the contact surface of sulphur and electrolyte
Product, further increase the specific discharge capacity of sulphur；Nitrogen-doped carbon will improve the utilization rate of sulphur, so as to improve the electric discharge specific volume of sulphur
Amount, improve the high rate performance of battery, while the nitrogen key in carbonnitrogen bond also can form stronger chemisorbed effect with polysulfide,
The loss of polysulfide is reduced, the coulombic efficiency of battery is improved and improves the cycle performance of battery.Novel material structure each side
The cooperative effect in face will significantly improve specific discharge capacity, high rate performance and the cycle performance of material.
Claims (4)
1. a kind of lithium-sulfur cell composite anode material of one-dimensional N doping double-layer carbon shell/sulphur, it is characterized in that：For with nitrogen-doped carbon
Elongated double-layer carbon housing made of material, the elemental sulfur of nanop articulate form is dispersed between double-layer carbon shell.
A kind of 2. system of the lithium-sulfur cell composite anode material of one-dimensional N doping double-layer carbon shell/sulphur as claimed in claim 1
Preparation Method, it is characterized in that comprising the following steps：
(1) by FeCl3And NH4H2PO4According to mol ratio 20:1~100:It is put into after 1 mixing in hydrothermal reaction kettle, 200~250
Heated 8~30 hours under the conditions of degree, conventional filtration cleans after being cooled to room temperature, obtains the one-dimensional Fe with hollow structure2O3Rod
Presoma；The Fe that will be obtained2O3Presoma is distributed in the polymer monomer aqueous solution and stirred 2~4 hours, conventional filtration cleaning,
Vacuum drying obtains one-dimensional PDA@Fe2O3 composites；
(2) resulting composite is put into and be connected with the tube furnace of protection gas, high temperature cabonization 1~4 hour, temperature 900
~1200 DEG C, then products therefrom be put into the aqueous hydrochloric acid solution of 0.1 mol/L and etch 4~6 hours, conventional cleaning filtering, very
Sky obtains one-dimensional N doping double-layer carbon shell after drying；
(3) by business sulphur powder and one-dimensional N doping double-layer carbon shell according to 1:1~3:1 mass ratio mixing, is then placed in closed
In container, vacuum is evacuated to as after 100~500Pa, 180~300 are risen to from room temperature with 2 degrees/min of heating rate
Degree, 10~20 hours are incubated, are cooled to 155 degree~160 degree, be incubated 10~20 hours, then with 20 degrees/min~50 degrees/min
Rate of temperature fall be cooled to room temperature and produce.
3. the preparation of the lithium-sulfur cell composite anode material of one-dimensional N doping double-layer carbon shell/sulphur according to claim 2
Method, it is characterized in that：The concentration of the polymer monomer aqueous solution described in step (1) is 0.5g~3g/L, and polymer monomer is salt
Sour dopamine.
4. the system of the lithium-sulfur cell composite anode material of one-dimensional N doping double-layer carbon shell/sulphur according to Claims 2 or 3
Preparation Method, it is characterized in that：Protection gas described in step (2) is one kind in nitrogen, argon hydrogen gaseous mixture or ammonia argon gas gaseous mixture,
The flow velocity of gas is the ml/min of 50 ml/mins~300.
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| CN201710913455.6A CN107732184A (en) | 2017-09-30 | 2017-09-30 | Lithium-sulfur battery composite anode material of one-dimensional N doping double-layer carbon shell/sulphur and preparation method thereof |
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| CN201710913455.6A CN107732184A (en) | 2017-09-30 | 2017-09-30 | Lithium-sulfur battery composite anode material of one-dimensional N doping double-layer carbon shell/sulphur and preparation method thereof |
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| CN201710913455.6A Pending CN107732184A (en) | 2017-09-30 | 2017-09-30 | Lithium-sulfur battery composite anode material of one-dimensional N doping double-layer carbon shell/sulphur and preparation method thereof |
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