CN108232189A - Cobalt metal organic frame sulfur loaded electrode material and its preparation method and application - Google Patents
Cobalt metal organic frame sulfur loaded electrode material and its preparation method and application Download PDFInfo
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- H—ELECTRICITY
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- H—ELECTRICITY
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Abstract
The invention discloses a kind of cobalt metal organic frame sulfur loaded electrode materials and its preparation method and application, and the preparation method carries out as steps described below:Cobalt salt, Trimesic acid and hydroxide are placed in deionized water, under agitation, 5~8 hours is kept the temperature in 180~200 DEG C, obtains pink colour turbid, the pink colour turbid is filtered, obtains cobalt metal organic frame.Gained cobalt metal organic frame with sulphur is uniformly mixed, obtains solid powder, in an inert atmosphere, the solid powder is warming up to 150~170 DEG C and keeps the temperature 10~12 hours, is down to 20~25 DEG C of room temperature naturally.The cobalt metal organic frame load sulfur materials that the preparation method of the present invention obtains can effectively limit the dissolving migration of polysulfide, and cobalt metal organic frame load sulfur materials, which are applied in lithium-sulfur cell, can improve lithium sulfur battery anode material specific capacity and cyclical stability.
Description
Technical field
The invention belongs to prepare lithium-sulfur cell field of material technology, a kind of cobalt metal organic frame load is related in particular to
Sulfur electrode material and its preparation method and application.
Background technology
Conventional lithium ion battery plays an important role in electronic product at present, however by its relatively low theoretical specific volume
The limitation of (150~200Wh/kg) is measured, lithium ion battery will be difficult to the long-term needs for meeting human development.And nowadays lithium sulphur is electric
Pond has attracted the research interest of more and more scientific researchers.This is because sulphur has higher specific capacity (1675mAh/
G), the theoretical energy density for lithium-sulfur cell being formed with lithium anode is about 2600Wh/kg, is the 3~5 of lithium ion battery
Times.Compared to common anode material for lithium-ion batteries (LiCoO2、LiMnO2、LiFeO4Deng), sulphur have derive from a wealth of sources, cost
The features such as low, safe, environmental-friendly is a kind of high-energy-density positive electrode with huge prospect, based on above-mentioned 2 points
Lithium-sulfur cell is the electrochemical energy storage system of great application prospect.However the active material utilization that lithium-sulfur cell still remains
The problems such as low, sulphur conductivity is extremely low, polysulfide dissolving migrates, cycle life is short, high rate performance is poor, self-discharge phenomenon is serious
Restrict the industrialization of its application.Therefore, it migrated to enhance the dissolving of the conductivity of anode sulphur, reduction polysulfide, improve lithium
The capacity and cyclical stability of sulphur battery, it is most important to research and develop novel lithium sulfur battery anode material.
Invention content
In view of the deficiencies of the prior art, the purpose of the present invention is to provide a kind of cobalt metal organic frame load sulfur materials
Preparation method, it is another object of the present invention is to provide a kind of cobalt metal organic frame load sulfur materials, the cobalt metal is organic
Frame load sulfur materials are applied to the specific capacity that lithium-sulfur cell can be improved in lithium-sulfur cell.
The technical scheme is that be achieved by following technical proposals.
A kind of preparation method of cobalt metal organic frame load sulfur materials, carries out as steps described below:
Step 1, cobalt salt, Trimesic acid and hydroxide are placed in deionized water, under agitation, in 180~
200 DEG C keep the temperature 5~8 hours, obtain pink colour turbid, and the pink colour turbid is filtered, obtains cobalt metal organic frame, wherein, institute
State take cobalt salt, Trimesic acid and hydroxide mass parts ratio be (5~7):(5~5.3):1;
In the above-mentioned technical solutions, the cobalt salt is cobalt chloride or cobalt nitrate, and the hydroxide is potassium hydroxide or hydrogen
Sodium oxide molybdena.
In the step 1, the ratios of the mass parts for taking cobalt salt, Trimesic acid and hydroxide for (5.3~
6.7):(5~5.1):1.
In the step 1, the ratio of the volume parts of deionized water and the mass fraction of Trimesic acid is (10~15):
1, wherein, the unit of the volume parts is mL, and the unit of the mass fraction is g.
Step 2, step 1 gained cobalt metal organic frame with sulphur is uniformly mixed, solid powder is obtained, in inert gas ring
Under border, the solid powder is warming up to 150~170 DEG C and keeps the temperature 10~12 hours, is down to 20~25 DEG C of room temperature naturally,
Wherein, the cobalt metal organic frame and the ratio of sulphur mass parts are 1:(1~3).
In the step 2, after the cobalt metal organic frame is uniformly mixed with sulphur, not a half hour is ground to, obtains institute
State solid powder.
In the step 2, the inert gas is argon gas.
In the step 2, heating rate is 4~8 DEG C/min.
In the step 2, after being cooled to room temperature, at least 5min is ground, 180~220 mesh sieve is crossed, obtains the cobalt metal
Organic frame loads sulfur materials.
The cobalt metal organic frame load sulfur materials that above-mentioned preparation method obtains.
In the above-mentioned technical solutions, the cobalt metal organic frame load sulfur materials include:Cobalt metal organic frame and sulphur,
Wherein, pore structure is formed on the cobalt metal organic frame, the sulphur is embedded in the pore structure.
In the above-mentioned technical solutions, the cobalt metal organic frame load the content of sulphur in sulfur materials for 50~
77wt%.
A kind of application of above-mentioned cobalt metal organic frame load sulfur materials in lithium-sulfur cell specific capacity is improved.
In the above-mentioned technical solutions, the cobalt metal organic frame is loaded sulfur materials, acetylene black and binding agent PTFE to mix
Uniform, dropwise addition absolute ethyl alcohol is closed, allows it to roll into the smooth thin slice of 3~4mg, wherein, the cobalt metal organic frame is born
The mass parts ratio for carrying sulfur materials, acetylene black and binding agent PTFE is 5:(3.5~4.5):(0.8~1.2);By the smooth thin slice
The disk of a diameter of 1cm is cut into, as anode.
In the above-mentioned technical solutions, double trifluoromethanesulfonimide lithium solution of 1M are as electrolyte, metal lithium sheet conduct
To electrode, microporous polypropylene membrane is as diaphragm, the anode, electrolyte, diaphragm and to electrode composition CR2032 button lithiums sulphur electricity
Pond;In the current density of 100mA/g, the specific capacity of the CR2032 button lithium-sulfur cells is 640~910mAh/g, can be alleviated
Lithium-sulfur cell special capacity fade and raising lithium-sulfur cell cyclical stability.
Compared with the prior art, the cobalt metal organic frame load sulfur materials that preparation method of the invention obtains can be effective
Limitation polysulfide dissolving migration, cobalt metal organic frame load sulfur materials are applied in lithium-sulfur cell and can alleviate anode
The capacity attenuation caused by the dissolving of polysulfide migrates, improves lithium sulfur battery anode material specific capacity in material charge and discharge process
And cyclical stability.
Description of the drawings
Fig. 1 is that the cobalt metal organic frame of the present invention loads the XRD diagram of sulfur materials;
Fig. 2 (a) is the scanning electron microscope image of original Co-MOF, and Fig. 2 (b) is the scanning electricity of 155 DEG C of treated Co-MOF
Mirror image, scanning electron microscope images of the Fig. 2 (c) for Co-MOF1S1, scanning electron microscope images of the Fig. 2 (d) for Co-MOF1S2, Fig. 2 (e)
Scanning electron microscope image for Co-MOF1S3;
Fig. 3 is thermogravimetric analysis (TGA) image of S, Co-MOF1S1, Co-MOF1S2 and Co-MOF1S3;
Fig. 4 is charge and discharge of Co-MOF1S1, Co-MOF1S2 and Co-MOF1S3 electrode when current density is 100mA/g
Cyclic curve;
Fig. 5 is that the first charge-discharge of Co-MOF1S1, Co-MOF1S2 and Co-MOF1S3 under 100mA/g current densities is bent
Line;
Fig. 6 is that rate charge-discharge of the Co-MOF1S2 composite samples respectively under 100,400 and 800mA/g current densities is bent
Line.
Specific embodiment
In the specific embodiment of the present invention, cobalt nitrate (Co (NO3)2·6H2O, analysis are pure) it buys from Tianjin good fortune morning
Chemical reagent factory, Trimesic acid (C9H6O6, analyze pure) and it buys from the Tianjin sky over the river and unifies Science and Technology Ltd., potassium hydroxide
It is bought with sodium hydroxide (KOH, NaOH analysis are pure) from Tianjin Fengchuan Chemical Reagent Science & Technology Co., Ltd..Acetylene black, polytetrafluoro
Ethylene (PTFE) and absolute ethyl alcohol are purchased from the Tianjin sky over the river and unify Science and Technology Ltd..Sulphur uses sublimed sulfur (AR), and purchase is certainly
The sky over the river unifies Science and Technology Ltd..
In the present invention, cobalt metal organic frame load sulfur materials can be expressed as Co-MOF S composite materials, Co-MOF S
The preparation of composite electrode and electrochemical property test condition are as follows:
Cobalt metal organic frame load sulfur materials are pulverized and acetylene black and binding agent PTFE in mass ratio 5:4:1 ratio
Example makes electrode slice.The process for making electrode slice is as follows:By load weighted cobalt metal organic frame load sulfur materials, acetylene black and
Binding agent PTFE is mixed, and 3~4 drop absolute ethyl alcohols are added dropwise, roll into the smooth thin of 3~4mg using stainless steel bar on stainless steel
Piece is cut into the disk of diameter 1cm or so with scissors, as anode.The double trifluoromethanesulfonimide lithiums (LiTFSI) of 1M (mol/L)
Solution (lark prestige Science and Technology Ltd.) as electrolyte, wherein, contain volume ratio in double trifluoromethanesulfonimide lithium solution
It is 1:1 1,3- dioxolanes and glycol dimethyl ether and 1% (mass volume ratio) LiNO3.(polypropylene is micro- by Cegard2300
Pore membrane) as diaphragm, metal lithium sheet is used as to electrode and reference electrode, and CR2032 buttons are formed in the glove box full of argon gas
Lithium-sulfur cell.The LAND CT2001A battery test systems test cobalt metal organic frame sulfur loaded that Jin Nuo companies produce in Wuhan
The charge-discharge performance of material, constant current charge-discharge current density are 100mA/g, voltage range 1.5-3.0V.It is in current density
100th, rate charge-discharge test, voltage range 1.5- are carried out to cobalt metal organic frame load sulfur materials under 400 and 800mA/g
3.0V.The environment temperature of charge and discharge is 25 DEG C of constant temperatures.
In the specific embodiment of the present invention, Rigaku D/MAX2500V/PC types X-ray diffractometer analysis material is selected
Material phase composition (using Cu/K alpha rays,);Material is scanned using FEI Nova Nano SEM 2300
Electronic Speculum tests (accelerating potential 15.0kV).
Technical scheme of the present invention is described in detail with reference to the accompanying drawings and examples.
Embodiment 1
A kind of preparation method of cobalt metal organic frame load sulfur materials, carries out as steps described below:
Step 1,4g cobalt chlorides, 3.8g Trimesic acids and 0.75g potassium hydroxide are placed in 250ml round-bottomed flasks, added
Enter 50mL deionized waters, under agitation, keep the temperature 5 hours in 180 DEG C, pink colour turbid is obtained, by pink colour turbid filter paper mistake
Filter, obtains cobalt metal organic frame (following original Co-MOF).
Step 2, step 1 gained cobalt metal organic frame with sublimed sulfur is mixed, grinds half an hour, obtain solid powder,
Wherein, cobalt metal organic frame and the ratio of sulphur mass parts are 1:1.Solid powder is transferred to corundum boat, corundum boat is placed in pipe
In formula stove, under Ar compression rings border, solid powder is warming up to 155 DEG C with the heating rate of 4 DEG C/min and keeps the temperature 10 hours, it is natural
20~25 DEG C of room temperature is down to, 5min is ground after taking-up, crosses 200 mesh sieve, obtains cobalt metal organic frame load sulfur materials (i.e. Co-
MOF1S1)。
Embodiment 2
A kind of preparation method of cobalt metal organic frame load sulfur materials, carries out as steps described below:
Step 1,5g cobalt nitrates, 3.8g Trimesic acids and 0.75g potassium hydroxide are placed in 250ml round-bottomed flasks, added
Enter 50mL deionized waters, under agitation, keep the temperature 5 hours in 180 DEG C, pink colour turbid is obtained, by pink colour turbid filter paper mistake
Filter, obtains cobalt metal organic frame.
Step 2, step 1 gained cobalt metal organic frame with sublimed sulfur is mixed, grinds half an hour, obtain solid powder,
Wherein, cobalt metal organic frame and the ratio of sulphur mass parts are 1:2.Solid powder is transferred to corundum boat, corundum boat is placed in pipe
In formula stove, under Ar compression rings border, solid powder is warming up to 155 DEG C with the heating rate of 4 DEG C/min and keeps the temperature 10 hours, it is natural
20~25 DEG C of room temperature is down to, 5min is ground after taking-up, crosses 200 mesh sieve, obtains cobalt metal organic frame load sulfur materials (i.e. Co-
MOF1S2)。
Embodiment 3
A kind of preparation method of cobalt metal organic frame load sulfur materials, carries out as steps described below:
Step 1,5g cobalt nitrates, 3.8g Trimesic acids and 0.75g sodium hydroxides are placed in 250ml round-bottomed flasks, added
Enter 50m L deionized waters, under agitation, keep the temperature 8 hours in 180 DEG C, pink colour turbid is obtained, by pink colour turbid filter paper mistake
Filter, obtains cobalt metal organic frame.
Step 2, step 1 gained cobalt metal organic frame with sublimed sulfur is mixed, grinds half an hour, obtain solid powder,
Wherein, cobalt metal organic frame and the ratio of sulphur mass parts are 1:3.Solid powder is transferred to corundum boat, corundum boat is placed in pipe
In formula stove, under Ar compression rings border, solid powder is warming up to 155 DEG C with the heating rate of 4 DEG C/min and keeps the temperature 10 hours, it is natural
20~25 DEG C of room temperature is down to, 5min is ground after taking-up, crosses 200 mesh sieve, obtains cobalt metal organic frame load sulfur materials (i.e. Co-
MOF1S3)。
Embodiment 4
A kind of preparation method of cobalt metal organic frame, carries out as steps described below:By 5g cobalt nitrates, 3.8g mesitylene first
Acid and 0.75g sodium hydroxides are placed in 250ml round-bottomed flasks, add in 50mL deionized waters, under agitation, in 180 DEG C of guarantors
Temperature 8 hours, obtains pink colour turbid, pink colour turbid with filter paper is filtered, obtains cobalt metal organic frame.
Cobalt metal organic frame is ground into half an hour, corundum boat is transferred to, corundum boat is placed in tube furnace, in Ar compression rings
Under border, solid powder is warming up to 155 DEG C with the heating rate of 4 DEG C/min and keeps the temperature 10 hours, is down to room temperature 20~25 naturally
DEG C, it grinds 5min after taking-up, crosses 200 mesh sieve, obtaining 155 DEG C treated cobalt metal organic frame, (i.e. 155 DEG C treated
Co-MOF)。
A, polycrystalline X-ray powder diffraction (XRD) analysis of sample
Fig. 1 is Co-MOF1S3, Co-MOF1S2, Co-MOF1S1, S, 155 DEG C of treated Co-MOF and original Co-MOF
The XRD diagram picture of (without heat treatment).As seen from the figure, original Co-MOF, 155 DEG C of treated Co-MOF, Co-MOF1S1,
Co-MOF1S2 and Co-MOF1S3 is crystalline state, and 155 DEG C treated that Co-MOF still remains crystalline structure.Sulphur with
Co-MOF does not occur new crystalline phase with different quality after compound, and can find out the characteristic peak of apparent sulphur.
B, the morphology analysis of sample
Fig. 2 (a) is the scanning electron microscope image (SEM) of original Co-MOF, and Fig. 2 (b) is 155 DEG C of treated Co-MOF materials
Scanning electron microscope image, Fig. 2 (c), 2 (d) and 2 (e) are followed successively by the SEM figures of Co-MOF1S1, Co-MOF1S2 and Co-MOF1S3
Picture.By Fig. 2 (a) it is found that Co-MOF has rough surface and pore structure in itself, sulphur can be fixed in hole;In Fig. 2 (b), warp
The aperture structure for crossing the Co-MOF itself of heat treatment is not destroyed, and is formed with some more obvious holes after the heating instead
Gauge structure;In Fig. 2 (c), 2 (d) in 2 (e), it can clearly see that Co-MOF surfaces cover a thick layer of sulphur, and
And it is no longer able to see the aperture of Co-MOF in figure, this may be that sulphur has been filled with the hole of Co-MOF and suffers, and then say
Bright Co-MOF can fix sulphur and sulphur is prevented to be dissolved into electrolyte well.Across comparison Fig. 2 (c), 2 (d) and 2 (e), can be with
It was found that with the raising of sulphur mass ratio, the load capacity of sulphur is increasing, and the crystal structure so as to cause Co-MOF in Fig. 2 (e) has
Some are destroyed.
C, the thermogravimetric analysis of sample
Fig. 3 is thermogravimetric analysis (TGA) image of S, Co-MOF1S1, Co-MOF1S2 and Co-MOF1S3.We can from figure
To find out, the sulphur load capacity of Co-MOF1S1, Co-MOF1S2 and Co-MOF1S3 are respectively 50.2%, 67.7% and 76.8%.It is pure
Sulphur loses load completely in 330 DEG C or so complete agravities, Co-MOF1S1, Co-MOF1S2 and Co-MOF1S3 at 320 DEG C or so
Sulphur, and the weightlessness of weight-loss curve and bright sulfur of Co-MOF1S1, Co-MOF1S2 and Co-MOF1S3 composite material before 330 DEG C is bent
Line fits like a glove, this is preferably demonstrated before 330 DEG C, the weight that Co-MOF1S1, Co-MOF1S2 and Co-MOF1S3 are lost
The completely quality of its sulphur loaded.
D, the electrochemical property test of sample
By Co-MOF1S1 (1 in Fig. 4:1 curve), Co-MOF1S2 is (1 in Fig. 4:2 curves) and Co-MOF1S3 (1 in Fig. 4:3
Curve) it is prepared into CR2032 button lithium-sulfur cells respectively.Fig. 4 is CR2032 button lithium-sulfur cells Co-MOF1S1, Co-MOF1S2
With charge and discharge cycles curve of the Co-MOF1S3 electrodes when current density is 100mA/g.As shown in Figure 4, although first week specific volume
Co-MOF1S1 is measured higher than Co-MOF1S2 higher than Co-MOF1S3, but since the sulphur load capacity of Co-MOF1S1 is small, thus 5 weeks with
The specific capacity of Co-MOF1S1 composite materials maintains 750mA h/g afterwards, the stabilization specific capacity 910mA much smaller than Co-MOF1S2
h/g.Compared with Co-MOF1S2 composite materials, the specific capacity of Co-MOF1S3 composite materials is relatively smaller, only 640mA h/g.
Scheme with reference to the SEM of Co-MOF1S3, illustrate to be supported on organic frame surface due to a large amount of sulphur, destroy metal organic frame
Structure cannot preferably play the role of limiting sulphur and polysulfide dissolving so as to cause frame.Therefore, Co-MOF1S2 is compound
The cyclical stability of material is best, this is because MOFS2 composite materials can either keep metal organic frame well
Structure (is not caved in), prevents the dissolving of polysulfide from migrating, and can have enough sulphur loads, is alleviated to a certain extent
The capacity attenuation and bulk effect of electrode material.
Fig. 5 for Co-MOF1S1, Co-MOF1S2 and Co-MOF1S3 composite material under 100mA/g current densities for the first time
Charging and discharging curve.It is to lose electronics from polysulfide to become in the charging platform of 2.2V or so it can be seen that in the charging stage
Caused by elemental sulfur.Two typical discharge platforms 2.3 and 2.1V in discharge curve are due to S8More vulcanizations to long-chain
Object changes and long-chain polysulphides become short and small sulfide and change what is formed.The charging platform of Co-MOF1S2 composite materials
It to be grown compared with the platform of Co-MOF1S1, Co-MOF1S3, this shows that the specific capacity of Co-MOF1S2 composite sample electrodes is higher than
Co-MOF1S1、Co-MOF1S3。
Fig. 6 is that rate charge-discharge of the Co-MOF1S2 composite samples respectively under 100,400,800mA/g current densities is bent
Line.As seen from the figure, Co-MOF1S2 composite samples can still have preferable specific capacity under higher current density, and
In the current density for being restored to 100mA/g, specific capacity can still be kept, and it is preferable that this illustrates that MOFS2 composite materials have
High rate performance.
Parameters in technical solution of the present invention are adjusted, can reach the property consistent with the above embodiment of the present invention.
This research promotes plan (No.52XC1502) and Tianjin high by Tianjin Normal University's Middl-age and youth faculty Academic innovations
Schools' innovation team's training plan (No.TD12-5038) is waited to subsidize.
Illustrative description has been done to the present invention above, it should explanation, in the situation for the core for not departing from the present invention
Under, any simple deformation, modification or other skilled in the art can not spend the equivalent replacement of creative work equal
Fall into protection scope of the present invention.
Claims (10)
1. a kind of preparation method of cobalt metal organic frame load sulfur materials, which is characterized in that carry out as steps described below:
Step 1, cobalt salt, Trimesic acid and hydroxide are placed in deionized water, under agitation, in 180~200 DEG C
Heat preservation 5~8 hours, obtains pink colour turbid, and the pink colour turbid is filtered, obtains cobalt metal organic frame, wherein, it is described to take cobalt
The ratio of salt, Trimesic acid and hydroxide mass parts is (5~7):(5~5.3):1;
Step 2, step 1 gained cobalt metal organic frame with sulphur is uniformly mixed, solid powder is obtained, in inert gas environment
Under, the solid powder is warming up to 150~170 DEG C and keeps the temperature 10~12 hours, is down to 20~25 DEG C of room temperature naturally,
In, the ratio of the cobalt metal organic frame and sulphur mass parts is 1:(1~3).
2. preparation method according to claim 1, which is characterized in that the cobalt salt be cobalt chloride or cobalt nitrate, the hydrogen
Oxide is potassium hydroxide or sodium hydroxide.
3. preparation method according to claim 1, which is characterized in that described to take cobalt salt, mesitylene in the step 1
The ratio of the mass parts of formic acid and hydroxide is (5.3~6.7):(5~5.1):1;The volume parts of the deionized water with
The ratio of the mass fraction of three benzoic acid is (10~15):1, wherein, the unit of the volume parts is mL, the mass fraction
Unit is g.
4. preparation method according to claim 1, which is characterized in that in the step 2, the cobalt metal organic frame
After uniformly being mixed with sulphur, not a half hour is ground to, obtains the solid powder;The inert gas is argon gas;Heating rate is 4
~8 DEG C/min.
5. preparation method according to claim 1, which is characterized in that in the step 2, after being cooled to room temperature, grinding
At least 5min crosses 180~220 mesh sieve, obtains the cobalt metal organic frame load sulfur materials.
6. the cobalt metal organic frame load sulfur materials that preparation method as claimed in any one of claims 1 to 5, wherein obtains.
7. cobalt metal organic frame according to claim 6 loads sulfur materials, which is characterized in that the cobalt metal has machine frame
Frame load sulfur materials include:Cobalt metal organic frame and sulphur, wherein, it is formed with hole knot on the cobalt metal organic frame
Structure, the sulphur are embedded in the pore structure;The cobalt metal organic frame load the content of sulphur in sulfur materials for 50~
77wt%.
8. application of the cobalt metal organic frame load sulfur materials in lithium-sulfur cell specific capacity is improved as claimed in claims 6 or 7.
9. application according to claim 8, which is characterized in that the cobalt metal organic frame is loaded into sulfur materials, acetylene
Black and binding agent PTFE is uniformly mixed, and absolute ethyl alcohol is added dropwise, allows it to roll into the smooth thin slice of 3~4mg, will be described smooth
Thin slice is cut into the disk of a diameter of 1cm, as anode, wherein, the cobalt metal organic frame loads sulfur materials, acetylene black and glues
The mass parts ratio for tying agent PTFE is 5:(3.5~4.5):(0.8~1.2).
10. application according to claim 9, which is characterized in that double trifluoromethanesulfonimide lithium solution of 1M are as electricity
Liquid is solved, metal lithium sheet is used as to electrode, and microporous polypropylene membrane is used as diaphragm, the anode, electrolyte, diaphragm and to electrode composition
CR2032 button lithium-sulfur cells;In the current density of 100mA/g, the specific capacities of the CR2032 button lithium-sulfur cells for 640~
910mA h/g can alleviate lithium-sulfur cell special capacity fade and improve lithium-sulfur cell cyclical stability.
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CN111446451A (en) * | 2020-04-07 | 2020-07-24 | 绍兴诺鼎卫浴洁具股份有限公司 | Co-Ni carbon material loaded g-C3N4-rGO positive electrode material of lithium-sulfur battery and preparation method thereof |
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CN111446451A (en) * | 2020-04-07 | 2020-07-24 | 绍兴诺鼎卫浴洁具股份有限公司 | Co-Ni carbon material loaded g-C3N4-rGO positive electrode material of lithium-sulfur battery and preparation method thereof |
CN111533178A (en) * | 2020-04-30 | 2020-08-14 | 江苏师范大学 | Method for preparing Zn-Co-S composite material based on multi-metal organic framework compound |
CN113782728A (en) * | 2021-09-15 | 2021-12-10 | 浙江王点科技有限公司 | Preparation method and application of cobalt Prussian blue analogue/carbon nano tube composite material |
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