CN109888153A - A kind of low-melting-point metal modification composite diaphragm and preparation method thereof for lithium-sulfur cell - Google Patents
A kind of low-melting-point metal modification composite diaphragm and preparation method thereof for lithium-sulfur cell Download PDFInfo
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Abstract
The low-melting-point metal modification composite diaphragm and preparation method thereof that the present invention provides a kind of for lithium-sulfur cell, belongs to lithium-sulfur cell technical field.Composite diaphragm is modified provided by the present invention for the low-melting-point metal of lithium-sulfur cell, including basilar partition and the low-melting-point metal porous carbon composite for being coated on its surface, the low-melting-point metal porous carbon composite includes porous carbon materials matrix and the low-melting-point metal that is carried in the porous carbon materials matrix pore.The present invention is by the way that low-melting-point metal to be injected into porous carbon materials, not only make porous carbon materials that there is high conductivity, can effectively transmit lithium ion, additionally it is possible to alleviate shuttle effect, the comprehensive electrochemical for effectively promoting battery, improves the cyclical stability and service life of lithium-sulfur cell.And preparation process is easy to operate, by using simple wet coating, can prepare the composite diaphragm material with high electric property, be adapted to carry out industrialized production.
Description
Technical field
The present invention relates to lithium-sulfur cell technical field more particularly to a kind of low-melting-point metal modification for lithium-sulfur cell are multiple
Close diaphragm and preparation method thereof.
Background technique
Lithium-sulfur cell recent years is by extensive concern.Because their own has the advantages such as low cost, high-energy density, quilt
It is considered the important candidate of next-generation energy storage device.But low high rate performance, poor cyclical stability restrict always
It is further applied.These problems are mainly due to (1) the low electronic conductivity of sulphur；(2) what is generated in charge and discharge process is more
Lithium sulfide dissolves in the electrolytic solution, the shuttle effect of generation；(3) lithium anode cyclical stability is poor.Wherein, shuttle effect is
Most intractable in lithium-sulfur cell is also sixty-four dollar question.
So far, the shuttle effect being made to solve in lithium-sulfur cell has been there are various ways.Wherein, simply and effectively square
Formula is to coat one layer of porous carbon materials in traditional membrane surface.This carbon material has two aspect effects: (1) physics hinders more
The free diffusing of lithium sulfide improves the cyclical stability of battery to a certain extent；(2) the upper layer collector as sulphur anode,
More lithium sulfides of capture are recycled again, improve the utilization rate of sulphur.But the aperture in porous carbon materials is larger, Bu Nengyou
The obstruction polysulfide of effect is diffused into cathode side, causes lithium-sulfur cell cyclical stability poor, service life is short.
Summary of the invention
In consideration of it, the low-melting-point metal that the purpose of the present invention is to provide a kind of for lithium-sulfur cell modify composite diaphragm and
Preparation method.Low-melting-point metal provided by the invention modifies composite diaphragm, can hinder the free diffusing of polysulfide, improves
Shuttle effect is effectively relieved in the transmission of lithium ion, improves lithium-sulfur cell cyclical stability and service life.
In order to achieve the above-mentioned object of the invention, the present invention the following technical schemes are provided:
A kind of low-melting-point metal modification composite diaphragm for lithium-sulfur cell, including basilar partition and is coated on its surface
Low-melting-point metal porous carbon composite, the low-melting-point metal porous carbon composite include porous carbon materials matrix and load
Low-melting-point metal in the porous carbon materials matrix pore.
Preferably, the low-melting-point metal porous carbon composite with a thickness of 1~30 μm.
Preferably, the mass ratio of low-melting-point metal and porous carbon materials is in the low-melting-point metal porous carbon composite
0.05~1:1.
Preferably, the low-melting-point metal includes one of glass putty, zinc powder and aluminium powder or a variety of.
The present invention also provides the low-melting-point metal modification composite diaphragms that lithium-sulfur cell is used for described in above-mentioned technical proposal
Preparation method, comprising the following steps:
It is heated in protective gas after low-melting-point metal is mixed with porous carbon materials, obtains low-melting-point metal/porous carbon
Material blends；
After the low-melting-point metal/porous carbon materials mixture, adhesive and solvent are mixed, it is coated on basilar partition
On, it obtains modifying composite diaphragm for the low-melting-point metal of lithium-sulfur cell.
Preferably, the mass ratio of the low-melting-point metal/porous carbon materials mixture and adhesive is 1:0.1~1.
Preferably, gained slurry consolidates after the low-melting-point metal/porous carbon materials mixture, adhesive and solvent mix
Content is 25%~75%.
Preferably, the heating rate of the heating is 1~15 DEG C/min.
Preferably, the final temperature of the heating is 200~1000 DEG C.
Preferably, the soaking time of the final temperature is 1~48h.
The present invention provides a kind of low-melting-point metals for lithium-sulfur cell to modify composite diaphragm, including basilar partition and painting
For cloth in the low-melting-point metal porous carbon composite on its surface, the low-melting-point metal porous carbon composite includes porous carbon
Material matrix and the low-melting-point metal being carried in the porous carbon materials matrix pore.The present invention is by injecting low-melting-point metal
Into porous carbon materials, makes porous carbon materials that there is high conductivity, can effectively transmit lithium ion, while low-melting-point metal is also
The active force between porous carbon materials and polysulphide molecules can be enhanced, polysulphide molecules are adsorbed, it is hindered to be freely spread to
Shuttle effect is alleviated in cathode side, and it is insufficient to polysulfide obstructing capacity scarce effectively to make up conventional porous carbon materials diaphragm
Point improves the cyclical stability and service life of lithium-sulfur cell to promote the comprehensive electrochemical of battery.And in the present invention
In, after low-melting-point metal is injected into porous carbon materials, the specific surface area of carbon material can be reduced to a certain extent, added
A small amount of adhesive can reach better bond effect.The experimental results showed that low-melting-point metal composite diaphragm provided by the invention
The reversible capacity of 800~803mAh/g is still maintained after circulation 200 times, and after 2C circulation 200 times capacity according to
It is so able to maintain 78% or more, coulombic efficiency is close to 100%, and capacity still possesses initial capacity after carrying out 500 charge and discharge
80%.
Meanwhile preparation process provided by the invention is easy to operate, without preparing complicated compound sulfur electrode, by using letter
Single wet coating, can prepare the composite diaphragm material with high electric property, be adapted to carry out industrialized production.
Detailed description of the invention
The present invention will be further described in detail below with reference to the accompanying drawings and specific embodiments.
Fig. 1 is SEM figure of the low-melting-point metal tin/porous carbon materials made from embodiment 1 under low enlargement ratio；
Fig. 2 is that low-melting-point metal tin made from embodiment 1 modifies SEM figure of the composite diaphragm under high magnification；
Fig. 3 is the cycle performance figure that low-melting-point metal tin made from embodiment 1 modifies that composite diaphragm is applied to lithium-sulfur cell；
Fig. 4 is that low-melting-point metal aluminium made from embodiment 2 modifies composite diaphragm and the conventional carbon diaphragm that applies is respectively applied to lithium
Cycle performance figure in sulphur battery；
Fig. 5 is the cycle performance figure that the Zinc modified composite diaphragm of low-melting-point metal made from embodiment 3 is applied to lithium-sulfur cell.
Specific embodiment
The present invention provides a kind of low-melting-point metals for lithium-sulfur cell to modify composite diaphragm, including basilar partition and painting
For cloth in the low-melting-point metal porous carbon composite on its surface, the low-melting-point metal porous carbon composite includes porous carbon
Material matrix and the low-melting-point metal being carried in the porous carbon materials matrix pore.
In the present invention, the thickness of the low-melting-point metal porous carbon composite is preferably 1~30 μm, further preferably
It is 10~20 μm.
In the present invention, in the low-melting-point metal porous carbon composite low-melting-point metal and porous carbon materials quality
Than being preferably 0.05~1:1, further preferably 0.1~0.8:1, more preferably 0.4~0.6:1.
In the present invention, the low-melting-point metal preferably includes one of glass putty, zinc powder and aluminium powder or a variety of；It is described more
Hole carbon material preferably includes one or more in porous graphene, porous carbon nanotube and porous acetylene black.The present invention is to described
The specific partial size and source of low-melting-point metal and porous carbon materials do not have special restriction, using commercial product well known in the art
?.
The present invention also provides the low-melting-point metal modification composite diaphragms that lithium-sulfur cell is used for described in above-mentioned technical proposal
Preparation method, comprising the following steps:
It is heated in protective gas after low-melting-point metal is mixed with porous carbon materials, obtains low-melting-point metal/porous carbon
Material blends；
After the low-melting-point metal/porous carbon materials mixture, adhesive and solvent are mixed, it is coated on basilar partition
On, it obtains modifying composite diaphragm for the low-melting-point metal of lithium-sulfur cell.
The present invention heats in protective gas after mixing low-melting-point metal with porous carbon materials, obtain low-melting-point metal/
Porous carbon materials mixture.
In the present invention, the mixing preferably ball milling mixing in the ball mill.In the present invention, the revolving speed of the ball milling is excellent
It is selected as 200~1000 revs/min, further preferably 400~900 revs/min, more preferably 500 revs/min；The ball milling
Time be preferably 1~10h, further preferably 4~9h, more preferably 5h.
In the present invention, the heating carries out preferably in tube furnace.
In the present invention, the protective gas preferably includes N2, Ar or He.
In the present invention, the heating rate of the heating is preferably 1~15 DEG C/min, further preferably 4~12 DEG C/
Min, more preferably 5~10 DEG C/min；The final temperature of the heating is preferably 200~1000 DEG C, further preferably 300~750
DEG C, more preferably 500~650 DEG C；The soaking time of the final temperature is preferably 1~48h, further preferably 4~36h, more excellent
It is selected as 12~20h.During heating, the low-melting-point metal enters in the hole of the porous carbon materials present invention.
After obtaining low-melting-point metal/porous carbon materials mixture, the present invention mixes the low-melting-point metal/porous carbon materials
It after closing object, adhesive and solvent mixing, is coated on basilar partition, obtains compound for the low-melting-point metal modification of lithium-sulfur cell
Diaphragm.
In the present invention, the mass ratio of the low-melting-point metal/porous carbon materials mixture and adhesive is preferably 1:0.1
~1, further preferably 1:0.3~0.7, more preferably 1:0.5.
In the present invention, gained slurry after the low-melting-point metal/porous carbon materials mixture, adhesive and solvent mixing
Solid content be preferably 25%~75%, further preferably 40%~60%, more preferably 50%.
In the present invention, the solvent preferably includes one of deionized water, NMP and isopropanol or a variety of；The base
Bottom diaphragm is preferably the PP or PE being commercialized；Described adhesive preferably includes one of SBR, CMC and PVDF or a variety of.This hair
The bright source to the solvent, basilar partition and adhesive does not have special restriction, is using commercial product well known in the art
It can.
In the present invention, the mixed sequence is preferably first by low-melting-point metal/porous carbon materials mixture and adhesive
After mixing, solvent is added.The present invention does not have special restriction to the mixed mode, the side routinely mixed using this field
Formula, it is specific as stirred.In the present invention, the revolving speed of the stirring is preferably 100~3500 revs/min, further excellent
It is selected as 200~2000 revs/min, more preferably 500~1000 revs/min；The time of the stirring is preferably 1~12h, into one
Step is preferably 2~8h.
In the present invention, the mode of the coating is preferably wet coating.Specific side of the present invention to the wet coating
Formula does not have special restriction, using wet coating mode well known to those skilled in the art.
After the completion of coating, the basilar partition after coating is preferably carried out drying and processing by the present invention, is obtained for lithium-sulfur cell
Low-melting-point metal modify composite diaphragm.
In the present invention, the temperature of the drying is preferably 40~100 DEG C, and further preferably 60~70 DEG C；The baking
The dry time is preferably 1~48h, further preferably 24~36h.
Below with reference to embodiment to provided by the present invention for lithium-sulfur cell low-melting-point metal modify composite diaphragm and its
Preparation method is described in detail, but they cannot be interpreted as limiting the scope of the present invention.
Embodiment 1
(1) 0.5g metallic tin powder and 4.5g porous graphene are put into ball mill, are 400 revs/min in revolving speed
Under the conditions of, ball milling 4 hours, the mixture of low-melting-point metal tin powder and porous carbon materials is made.
(2) mixture that step (1) obtains is put into tube furnace, under protection of argon gas, with the heating rate of 5 DEG C/min
300 DEG C are warming up to, 4 hours is kept the temperature, obtains low-melting-point metal tin/porous carbon materials mixture.
(3) 2g PVDF is weighed, 70mL is added in low-melting-point metal tin/porous carbon materials mixture that 8g step (2) obtains
NMP stirred with blender, revolving speed be 800 revs/min, stir 8 hours.
(4) mixed slurry prepared in step (3) is coated on PP diaphragm, control coating layer thickness is 20 μm, 60
Under the conditions of DEG C, drying obtains low-melting-point metal tin modification composite diaphragm after 24 hours.
Fig. 1 is SEM figure of the low-melting-point metal tin/porous carbon materials made from embodiment 1 under low enlargement ratio, Cong Tuzhong
As can be seen that low-melting-point metal tin is uniformly injected into porous carbon materials.
Fig. 2 is that low-melting-point metal tin made from embodiment 1 modifies SEM figure of the composite diaphragm under high magnification, from figure
In as can be seen that metallic tin and the porous carbon bed of material are uniformly distributed, diaphragm coating layer thickness is 20 μm.
The low-melting-point metal tin modification composite diaphragm being prepared using embodiment 1 prepares lithium-sulfur cell as diaphragm, and
The cycle performance test of lithium-sulfur cell is carried out, test result is referring to Fig. 3.
The preparation of lithium-sulfur cell
Sulphur simple substance material, conductive black and PVDF 70:20:10 in mass ratio are mixed in NMP, coated in being on aluminium foil
Electrode, metal lithium sheet are to electrode, and the low-melting-point metal modification composite diaphragm that the present invention is prepared is as diaphragm, 1M
LiTFSI, 0.1M LiNO3(DOL and DME are solvent, volume ratio 1:1) is electrolyte, in the glove box of argon gas protection, group
Dress up button lithium-sulfur cell.
The cycle performance of lithium-sulfur cell is tested
At 30 DEG C of constant temperature, in the voltage range of 1.5~3.0V, charge-discharge test, circulation are carried out with the current density of 1C
500 times.Constant current charge-discharge test is carried out using Land battery test system.
Fig. 3 is the cycle performance figure that low-melting-point metal tin made from embodiment 1 modifies that composite diaphragm is applied to lithium-sulfur cell,
The reversible capacity of 803mAh/g is still maintained after the cycle performance curve of positive electrode is it is found that recycle 200 times as shown in Figure 3, and
And capacity is still able to maintain 78% or more after 2C circulation 200 times, coulombic efficiency has excellent close to 100%
Cyclical stability.
Embodiment 2
(1) 0.5g metal zinc and the porous carbon nanotube of 3.5g are put into ball mill, are 200 revs/min in revolving speed
Under the conditions of, ball milling 1 hour, the mixture of low-melting-point metal zinc powder and porous carbon materials is made.
(2) mixture that step (1) obtains is put into tube furnace, under helium protection, with the heating rate of 5 DEG C/min
750 DEG C are warming up to, 20h is kept the temperature, obtains low-melting-point metal zinc/porous carbon materials mixture.
(3) 1.5gPVDF is weighed, low-melting-point metal zinc/porous carbon materials mixture that 8.5g step (2) obtains is added
The NMP of 20mL is stirred with blender, and revolving speed is 500 revs/min, is stirred 12 hours.
(4) mixed slurry prepared in step (3) is coated on PE diaphragm, control coating layer thickness is 10 μm, 70
Under the conditions of DEG C, drying obtained the Zinc modified composite diaphragm of low-melting-point metal after 18 hours.
The preparation of lithium-sulfur cell
Sulphur simple substance material, conductive black and PVDF 70:20:10 in mass ratio are mixed in NMP, coated in being on aluminium foil
Electrode, metal lithium sheet are to electrode, and the low-melting-point metal modification composite diaphragm that the present invention is prepared is as diaphragm, 1M
LiTFSI, 0.1M LiNO3(DOL and DME are solvent, volume ratio 1:1) is electrolyte, in the glove box of argon gas protection, group
Dress up button lithium-sulfur cell.
The cycle performance of lithium-sulfur cell is tested
At 30 DEG C of constant temperature, in the voltage range of 1.5~3.0V, charge-discharge test, circulation are carried out with the current density of 1C
500 times.Constant current charge-discharge test is carried out using Land battery test system.
The Zinc modified composite diaphragm of low-melting-point metal being prepared using embodiment 2 prepares lithium-sulfur cell as diaphragm, and
The cycle performance test of lithium-sulfur cell is carried out, the PE diaphragm that comparative example uses commercially available conventional porous carbon materials to modify is lithium
Sulphur battery diaphragm, other conditions are same as described above, and test result is referring to fig. 4.
Fig. 4 is that the Zinc modified composite diaphragm of low-melting-point metal made from embodiment 2 and the conventional carbon diaphragm that applies are respectively applied to lithium
Cycle performance figure in sulphur battery, it can be seen from the figure that composite diaphragm prepared by the present invention carries out capacity after 500 charge and discharge
Still possess the 80% of initial capacity, and comparative example is assembled into lithium-sulfur cell using the PE diaphragm of Conventional porous carbon material modification, into
Capacity illustrates that the composite diaphragm can effectively inhibit shuttle effect into 65% for initial capacity after row 500 times circulations, improves sulphur electricity
The service life in pond.
Embodiment 3
(1) 1g metallic aluminium powder and the porous acetylene black of 2.5g are put into ball mill, the condition for being 900 revs/min in revolving speed
Under, ball milling 9 hours, the mixture of low-melting-point metal aluminium powder and porous carbon materials is made.
(2) mixture that step (1) obtains is put into tube furnace, under protection of argon gas, with the heating rate of 4 DEG C/min
650 DEG C are warming up to, 12h is kept the temperature, obtains low-melting-point metal aluminium/porous carbon materials mixture.
(3) 3g PVDF is weighed, low-melting-point metal aluminium/porous carbon materials mixture that 7.5g step (2) obtains is added
The NMP of 20mL is stirred with blender, and revolving speed is 200 revs/min, is stirred 2 hours.
(4) mixed slurry prepared in step (3) is coated on PP diaphragm, control coating layer thickness is 15 μm, 65
Under the conditions of DEG C, drying obtains low-melting-point metal aluminium modification composite diaphragm after 36 hours.
The preparation of lithium-sulfur cell
Sulphur simple substance material, conductive black and PVDF 70:20:10 in mass ratio are mixed in NMP, coated in being on aluminium foil
Electrode, metal lithium sheet are to electrode, and the low-melting-point metal modification composite diaphragm that the present invention is prepared is as diaphragm, 1M
LiTFSI, 0.1M LiNO3(DOL and DME are solvent, volume ratio 1:1) is electrolyte, in the glove box of argon gas protection, group
Dress up button lithium-sulfur cell.
The cycle performance of lithium-sulfur cell is tested
At 30 DEG C of constant temperature, in the voltage range of 1.5~3.0V, charge-discharge test, circulation are carried out with the current density of 1C
500 times.Constant current charge-discharge test is carried out using Land battery test system.
The low-melting-point metal aluminium modification composite diaphragm being prepared using embodiment 3 prepares lithium-sulfur cell as diaphragm, and
The cycle performance test of lithium-sulfur cell is carried out, test result is referring to Fig. 5.
Fig. 5 is the cycle performance figure that low-melting-point metal aluminium made from embodiment 3 modifies that composite diaphragm is applied to lithium-sulfur cell,
The reversible capacity of 800mAh/g is still maintained after the cycle performance curve of positive electrode is it is found that recycle 200 times as shown in Figure 5, and
And capacity is still able to maintain 78% or more after 2C circulation 200 times, coulombic efficiency has excellent close to 100%
Cyclical stability.
Embodiment 4
(1) 1.5g metallic tin powder and 3.5g porous graphene material are put into ball mill, are 800 revs/min in revolving speed
Under conditions of, ball milling 5 hours, the mixture of low-melting-point metal tin powder and porous graphene material is made.
(2) mixture that step (1) obtains is put into tube furnace, under nitrogen protection, with the heating rate of 4 DEG C/min
300 DEG C are warming up to, 12h is kept the temperature, obtains low-melting-point metal tin/porous graphene material blends.
(3) 2g CMC is weighed, low-melting-point metal tin/porous graphene material blends that 7.5g step (2) obtains are added
The isopropanol of 20mL is stirred with blender, and revolving speed is 210 revs/min, is stirred 2.5 hours.
(4) mixed slurry prepared in step (3) being coated on basilar partition, control coating layer thickness is 15 μm,
Under the conditions of 60 DEG C, drying obtains low-melting-point metal tin modification composite diaphragm after 20 hours.
The preparation of lithium-sulfur cell
Sulphur simple substance material, conductive black and PVDF 70:20:10 in mass ratio are mixed in NMP, coated in being on aluminium foil
Electrode, metal lithium sheet are to electrode, and the low-melting-point metal modification composite diaphragm that the present invention is prepared is as diaphragm, 1M
LiTFSI, 0.1M LiNO3(DOL and DME are solvent, volume ratio 1:1) is electrolyte, in the glove box of argon gas protection, group
Dress up button lithium-sulfur cell.
The cycle performance of lithium-sulfur cell is tested
At 30 DEG C of constant temperature, in the voltage range of 1.5~3.0V, charge-discharge test, circulation are carried out with the current density of 1C
500 times.Constant current charge-discharge test is carried out using Land battery test system.
Constant current charge-discharge test result is close with the test result of Examples 1 to 3, does not repeat one by one herein.
Embodiment 5
(1) 1.6g metal zinc and the porous acetylene black-materials of 3.4g are put into ball mill, are 750 revs/min in revolving speed
Under conditions of, ball milling 4.5 hours, the mixture of low-melting-point metal zinc powder and porous acetylene black-materials is made.
(2) mixture that step (1) obtains is put into tube furnace, under protection of argon gas, with the heating rate of 5 DEG C/min
650 DEG C are warming up to, 20h is kept the temperature, obtains low-melting-point metal zinc/porous acetylene black material blends.
(3) 1.5g SBR is weighed, the low-melting-point metal zinc that 7.5g step (2) obtains/porous acetylene black material blends adds
The ionized water for entering 20mL is stirred with blender, and revolving speed is 230 revs/min, is stirred 6 hours.
(4) mixed slurry prepared in step (3) being coated on basilar partition, control coating layer thickness is 17 μm,
Under the conditions of 60 DEG C, drying obtained the Zinc modified composite diaphragm of low-melting-point metal after 10 hours.
The preparation of lithium-sulfur cell
Sulphur simple substance material, conductive black and PVDF 70:20:10 in mass ratio are mixed in NMP, coated in being on aluminium foil
Electrode, metal lithium sheet are to electrode, and the low-melting-point metal modification composite diaphragm that the present invention is prepared is as diaphragm, 1M
LiTFSI, 0.1M LiNO3(DOL and DME are solvent, volume ratio 1:1) is electrolyte, in the glove box of argon gas protection, group
Dress up button lithium-sulfur cell.
The cycle performance of lithium-sulfur cell is tested
At 30 DEG C of constant temperature, in the voltage range of 1.5~3.0V, charge-discharge test, circulation are carried out with the current density of 1C
500 times.Constant current charge-discharge test is carried out using Land battery test system.
Constant current charge-discharge test result is close with the test result of Examples 1 to 3, does not repeat one by one herein.
It can be seen that low-melting-point metal composite diaphragm provided by the invention with good electrochemistry from above-mentioned experimental result
Performance, has excellent cyclical stability, and service life cycle is long.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of low-melting-point metal for lithium-sulfur cell modifies composite diaphragm, which is characterized in that including basilar partition and coating
Low-melting-point metal porous carbon composite on its surface, the low-melting-point metal porous carbon composite includes porous carbon materials
Matrix and the low-melting-point metal being carried in the porous carbon materials matrix pore.
2. modification composite diaphragm according to claim 1, which is characterized in that the low-melting-point metal porous carbon composite
With a thickness of 1~30 μm.
3. modification composite diaphragm according to claim 1 or 2, which is characterized in that the low-melting-point metal porous carbon is compound
The mass ratio of low-melting-point metal and porous carbon materials is 0.05~1:1 in material.
4. modification composite diaphragm according to claim 1, which is characterized in that the low-melting-point metal includes glass putty, zinc powder
With one of aluminium powder or a variety of.
5. the preparation method described in any one of Claims 1 to 4 for the low-melting-point metal modification composite diaphragm of lithium-sulfur cell,
It is characterized in that, comprising the following steps:
It is heated in protective gas after low-melting-point metal is mixed with porous carbon materials, obtains low-melting-point metal/porous carbon materials
Mixture；
After the low-melting-point metal/porous carbon materials mixture, adhesive and solvent are mixed, it is coated on basilar partition, obtains
Composite diaphragm is modified to the low-melting-point metal for lithium-sulfur cell.
6. preparation method according to claim 5, which is characterized in that the low-melting-point metal/porous carbon materials mixture
Mass ratio with adhesive is 1:0.1~1.
7. preparation method according to claim 5, which is characterized in that the low-melting-point metal/porous carbon materials mixture,
The solid content of gained slurry is 25%~75% after adhesive and solvent mixing.
8. preparation method according to claim 5, which is characterized in that the heating rate of the heating is 1~15 DEG C/min.
9. the preparation method according to claim 5 or 8, which is characterized in that the final temperature of the heating is 200~1000 DEG C.
10. preparation method according to claim 9, which is characterized in that the soaking time of the final temperature is 1~48h.
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