CN109378466A - A kind of preparation method and product of spherical shape lithium sulfur battery anode material - Google Patents
A kind of preparation method and product of spherical shape lithium sulfur battery anode material Download PDFInfo
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Abstract
The invention discloses a kind of preparation methods of spherical lithium sulfur battery anode material, and this method is by the way that sulphur presoma, carbon source, adhesive and polarity absorption additive to be distributed in water, and the spherical anode material with monodispersity is made in spray drying after mixing evenly.The invention also discloses the spherical lithium sulfur battery anode materials prepared by this method; the material is made of sulphur, carbon carrier, polymeric additive and polarity absorption additive, and the material present under a scanning electron microscope sulphur be uniformly distributed in it is internal as carbon nanotube is interlaced be entangled with made of spheric granules or sulphur be uniformly distributed in it is internal as graphene film is interlaced be entangled with made of monodispersity spheric granules.Preparation method of the present invention is simple, can quickly prepare lithium sulfur battery anode material, and spherical lithium sulfur battery anode material obtained has stronger adsorption capacity and electric conductivity, have monodispersity, energy payload sulphur, the conductive network of formation can be used conscientiously.
Description
Technical field
The present invention relates to a kind of preparation methods of spherical lithium sulfur battery anode material and the spherical lithium sulphur prepared with this method
Cell positive material.
Background technique
Lithium-sulfur cell theoretical energy density is up to 2600Wh kg-1, and positive active material elemental sulfur is cheap, it is nontoxic
It is harmless, it is based on above-mentioned advantage, lithium-sulfur cell has attracted the concern of many researchers, is expected to replace conventional lithium ion electricity at this stage
Pond becomes following high-energy density, long-life type secondary cell.
The development of lithium-sulfur cell technology faces many challenges, and one of main problem is since the insulating properties of elemental sulfur is unfavorable
In the transmission of electronics, so that active material sulphur utilization rate in charge and discharge process is very low.Another main problem is known as " shuttling and imitating
Answer ", positive sulphur generates Li when discharging2SnThe high-orders polysulfide such as (n=4~8) can be dissolved into the organic electrolyte of lithium-sulfur cell
In, and it is easy to diffuse to negative side, occurs self discharge reaction on cathode lithium surface, the product of self discharge migrates back positive and again again
It is newly oxidized, loops back and forth like this, the coulombic efficiency of battery is caused to reduce." shuttle effect " will lead to positive active material simultaneously
It is lost, and structure is caused to destroy, active material is detached from after repeatedly recycling with conductive agent, and it is poor to eventually lead to cyclical stability.
Currently, numerous researchs all concentrate on conductive carbon material answering sulphur by the modified carbon material of Heteroatom doping
It closes, forms the composite construction of " carbon packet sulphur " to improve lithium-sulfur cell performance.As Zhao Wei et al. (Nano letters, 2014,
14 (8): 4821-4827) preparation nitrogen-doped graphene-sulphur composite material, S@NG and Wang Jian et al. (Journal of
Power source, 2016,321:193-200) preparation N, S codope graphene shows to have polysulfide good
Chemical adsorption capacity, have a degree of improvement to the chemical property of lithium-sulfur cell.But currently used positive electrode
Preparation method is divided into two step of carbon material preparation process and carbon sulphur composite material preparation process.In the preparation of carbon sulphur composite material often
The problem of hot melt sulfur impregnated method, high temperature sulphur steam carry sulphur method etc. and are all inevitably present material clumps, and the sheet agglomerated
Matter is that carbon and sulphur form " sulphur packet carbon " type structure, this not only makes carbonaceous conductive network that can not play a role, while also to the later period
Electrode preparation brings problems.
Summary of the invention
The object of the present invention is to provide a kind of preparation methods of spherical lithium sulfur battery anode material, and not only method is simple, can
Lithium sulfur battery anode material is quickly prepared, and spherical lithium sulfur battery anode material obtained has stronger adsorption capacity and conduction
Property, there is monodispersity, while also wanting energy payload sulphur, the conductive network of formation can be used conscientiously.
Technical scheme is as follows:
A kind of preparation method of spherical shape lithium sulfur battery anode material, the preparation method is as follows: by sulphur presoma, carbon source, cohering
Agent and polarity absorption additive are distributed in water, are spray-dried after mixing evenly, and the spherical lithium sulphur electricity with monodispersity is made
Pond positive electrode.
Preferably, the sulphur presoma is one of ammonium polysulfide solution or thiosulfuric acid ammonium salt solution.By using can
The solution that dissolubility is prepared containing sulfosalt can accurately control load sulfur content by adjusting raw material proportioning as sulphur source.
Preferably, the carbon source be at least one of carbon nanotube or the dispersion liquid of graphene, dispersion solvent be water,
One of N-Methyl pyrrolidone, N,N-dimethylformamide.The present invention is with the carbon nanotube or graphene of well conducting
As carbon source, that constructs has excellent conductive network using carbon nanotube or graphene as the spherical structure of skeleton.
Preferably, the adhesive is water soluble polymer, and solute is polyacrylamide, polyvinylpyrrolidone, poly- second
Glycol, polyethylene glycol oxide, aqueous polyurethane, kayexalate, poly- 3,4-rthylene dioxythiophene-poly styrene sulfonate are molten
Liquid, phenolic resin, diallyl dimethyl ammoniumchloride, sodium alginate, sodium carboxymethylcellulose, chitosan, polylactic acid, xanthan
At least one of glue or guar gum.With water soluble polymer as balling-up adhesive, the stability of spheric granules is improved, is made
The spherical lithium sulfur battery anode material obtained spheric granules in electrode production process is not broken up or dusting.
Preferably, the polarity absorption additive is transition metal oxide nano particle or transition metal nitride nanometer
Particle；More preferably nano zine oxide, nano ferriferrous oxide, nano-titanium oxide, nanometer vanadic anhydride, nano aluminium oxide,
At least one of Nano titanium nitride, nano vanadium nitride.The addition of polarity absorption additive makes spherical lithium sulfur battery anode material
More lithium sulfides, fixed polysulfide can be effectively adsorbed, it is avoided to shuttle to negative side；And the addition of polarity absorption additive makes
Mutual exclusion between sphere material particle has monodispersity, does not agglomerate, and crushes, sieving process without the later period, greatly improves electricity
The efficiency of pole preparation.
Preferably, the spray drying temperature is 130~190 DEG C.
It is a further object to provide a kind of spherical lithium sulfur battery anode material, technical solution is as follows:
Spherical shape lithium sulfur battery anode material provided by the present invention is adsorbed by sulphur, carbon carrier, polymeric additive and polarity
Additive composition, the spherical shape lithium sulfur battery anode material present under a scanning electron microscope sulphur be uniformly distributed in it is internal by
Carbon nanotube is interlaced be entangled with made of monodispersity spheric granules or sulphur be uniformly distributed in it is internal mutual by graphene film
Monodispersity spheric granules made of being staggeredly entangled with.
The preparation method of spherical shape lithium sulfur battery anode material provided by the invention, preparation process is simple, only needs a step, a step
Spherical lithium sulfur battery anode material can be quickly made in spray drying, and low production cost, materials save.
Spherical shape lithium sulfur battery anode material provided by the invention, presentation sulphur is uniformly distributed in interior under a scanning electron microscope
Portion as carbon nanotube is interlaced be entangled with made of monodispersity spheric granules or present sulphur be uniformly distributed in it is internal by stone
Black alkene piece is interlaced be entangled with made of monodispersity spheric granules, grain structure is more stable, will not in electrode production process
Broken or dusting.Since the positive electrode forms excellent conductive network as carbon carrier using carbon nanotube or graphene, so that
The strong adsorption capacity of sulphur utilization rate with higher in charge and discharge process, inorganic nanoparticles can effectively inhibit more lithium sulfides
" shuttle effect " in charge and discharge process.Lithium sulfur battery anode material charge and discharge ratio with higher in charge and discharge process
Capacity and excellent cyclical stability have a good application prospect during the functionization of lithium-sulfur cell.
Detailed description of the invention
Fig. 1 is the stereoscan photograph of monodispersity spherical shape positive material for lithium-sulfur battery prepared by embodiment 1.
Fig. 2 is the stereoscan photograph of monodispersity spherical shape positive material for lithium-sulfur battery prepared by embodiment 5.
Fig. 3 is the stereoscan photograph of monodispersity spherical shape positive material for lithium-sulfur battery prepared by embodiment 10.
Fig. 4 is the stereoscan photograph of monodispersity spherical shape positive material for lithium-sulfur battery prepared by embodiment 15.
Fig. 5 is the stereoscan photograph of monodispersity spherical shape positive material for lithium-sulfur battery prepared by embodiment 20.
Specific embodiment
It elaborates below with reference to embodiment to the present invention.
Raw material title and mass fraction used in each embodiment are listed in Tables 1 and 2, wherein NMP is N- methyl
Pyrrolidones, DMF are n,N-Dimethylformamide.
Embodiment 1
The present embodiment prepares a kind of spherical positive material for lithium-sulfur battery, and steps are as follows:
By sulphur presoma, carbon source, adhesive, absorption additive in ingredient described in table 1 and ratio after mixing at 150 DEG C
Under the conditions of be spray-dried, collecting products therefrom is spherical positive material for lithium-sulfur battery.
Embodiment 2
A kind of method for preparing spherical positive material for lithium-sulfur battery, steps are as follows:
By sulphur presoma, carbon source, adhesive, absorption additive in ingredient described in table 1 and ratio after mixing at 135 DEG C
Under the conditions of be spray-dried, collecting products therefrom is spherical positive material for lithium-sulfur battery.
Embodiment 3
A kind of method for preparing spherical positive material for lithium-sulfur battery, steps are as follows:
By sulphur presoma, carbon source, adhesive, absorption additive in ingredient described in table 1 and ratio after mixing at 130 DEG C
Under the conditions of be spray-dried, collecting products therefrom is spherical positive material for lithium-sulfur battery.
Embodiment 4
A kind of method for preparing spherical positive material for lithium-sulfur battery, steps are as follows:
By sulphur presoma, carbon source, adhesive, absorption additive in ingredient described in table 1 and ratio after mixing at 140 DEG C
Under the conditions of be spray-dried, collecting products therefrom is spherical positive material for lithium-sulfur battery.
Embodiment 5
A kind of method for preparing spherical positive material for lithium-sulfur battery, steps are as follows:
By sulphur presoma, carbon source, adhesive, absorption additive in ingredient described in table 1 and ratio after mixing at 150 DEG C
Under the conditions of be spray-dried, collecting products therefrom is spherical positive material for lithium-sulfur battery.
Embodiment 6
A kind of method for preparing spherical positive material for lithium-sulfur battery, steps are as follows:
By sulphur presoma, carbon source, adhesive, absorption additive in ingredient described in table 1 and ratio after mixing at 135 DEG C
Under the conditions of be spray-dried, collecting products therefrom is spherical positive material for lithium-sulfur battery.
Embodiment 7
A kind of method for preparing spherical positive material for lithium-sulfur battery, steps are as follows:
By sulphur presoma, carbon source, adhesive, absorption additive in ingredient described in table 1 and ratio after mixing at 165 DEG C
Under the conditions of be spray-dried, collecting products therefrom is spherical positive material for lithium-sulfur battery.
Embodiment 8
A kind of method for preparing spherical positive material for lithium-sulfur battery, steps are as follows:
By sulphur presoma, carbon source, adhesive, absorption additive in ingredient described in table 1 and ratio after mixing at 150 DEG C
Under the conditions of be spray-dried, collecting products therefrom is spherical positive material for lithium-sulfur battery.
Embodiment 9
A kind of method for preparing spherical positive material for lithium-sulfur battery, steps are as follows:
By sulphur presoma, carbon source, adhesive, absorption additive in ingredient described in table 1 and ratio after mixing at 155 DEG C
Under the conditions of be spray-dried, collecting products therefrom is spherical positive material for lithium-sulfur battery.
Embodiment 10
A kind of method for preparing spherical positive material for lithium-sulfur battery, steps are as follows:
By sulphur presoma, carbon source, adhesive, absorption additive in ingredient described in table 1 and ratio after mixing at 135 DEG C
Under the conditions of be spray-dried, collecting products therefrom is spherical positive material for lithium-sulfur battery.
Embodiment 11
A kind of method for preparing spherical positive material for lithium-sulfur battery, steps are as follows:
By sulphur presoma, carbon source, adhesive, absorption additive in ingredient described in table 2 and ratio after mixing at 145 DEG C
Under the conditions of be spray-dried, collecting products therefrom is spherical positive material for lithium-sulfur battery.
Embodiment 12
A kind of method for preparing spherical positive material for lithium-sulfur battery, steps are as follows:
By sulphur presoma, carbon source, adhesive, absorption additive in ingredient described in table 2 and ratio after mixing at 140 DEG C
Under the conditions of be spray-dried, collecting products therefrom is spherical positive material for lithium-sulfur battery.
Embodiment 13
A kind of method for preparing spherical positive material for lithium-sulfur battery, steps are as follows:
By sulphur presoma, carbon source, adhesive, absorption additive in ingredient described in table 2 and ratio after mixing at 165 DEG C
Under the conditions of be spray-dried, collecting products therefrom is spherical positive material for lithium-sulfur battery.
Embodiment 14
A kind of method for preparing spherical positive material for lithium-sulfur battery, steps are as follows:
By sulphur presoma, carbon source, adhesive, absorption additive in ingredient described in table 2 and ratio after mixing at 190 DEG C
Under the conditions of be spray-dried, collecting products therefrom is spherical positive material for lithium-sulfur battery.
Embodiment 15
A kind of method for preparing spherical positive material for lithium-sulfur battery, steps are as follows:
By sulphur presoma, carbon source, adhesive, absorption additive in ingredient described in table 2 and ratio after mixing at 150 DEG C
Under the conditions of be spray-dried, collecting products therefrom is spherical positive material for lithium-sulfur battery.
Embodiment 16
A kind of method for preparing spherical positive material for lithium-sulfur battery, steps are as follows:
By sulphur presoma, carbon source, adhesive, absorption additive in ingredient described in table 2 and ratio after mixing at 135 DEG C
Under the conditions of be spray-dried, collecting products therefrom is spherical positive material for lithium-sulfur battery.
Embodiment 17
A kind of method for preparing spherical positive material for lithium-sulfur battery, steps are as follows:
By sulphur presoma, carbon source, adhesive, absorption additive in ingredient described in table 2 and ratio after mixing at 165 DEG C
Under the conditions of be spray-dried, collecting products therefrom is spherical positive material for lithium-sulfur battery.
Embodiment 18
A kind of method for preparing spherical positive material for lithium-sulfur battery, steps are as follows:
By sulphur presoma, carbon source, adhesive, absorption additive in ingredient described in table 2 and ratio after mixing at 150 DEG C
Under the conditions of be spray-dried, collecting products therefrom is spherical positive material for lithium-sulfur battery.
Embodiment 19
A kind of method for preparing spherical positive material for lithium-sulfur battery, steps are as follows:
By sulphur presoma, carbon source, adhesive, absorption additive in ingredient described in table 2 and ratio after mixing at 155 DEG C
Under the conditions of be spray-dried, collecting products therefrom is spherical positive material for lithium-sulfur battery.
Embodiment 20
A kind of method for preparing spherical positive material for lithium-sulfur battery, steps are as follows:
By sulphur presoma, carbon source, adhesive, absorption additive in ingredient described in table 2 and ratio after mixing at 135 DEG C
Under the conditions of be spray-dried, collecting products therefrom is spherical positive material for lithium-sulfur battery.
Performance test:
Electric performance test is carried out to spherical shape positive material for lithium-sulfur battery made from the various embodiments described above.
Test follows the steps below:
1, lithium-sulfur cell is made
Spherical positive material for lithium-sulfur battery obtained, conductive carbon black, Kynoar, N-Methyl pyrrolidone are pressed
Mass ratio 8:1:1:40 is placed in ball grinder, and ball milling 12h after uniform slurries at being applied on aluminium foil, and finally in a vacuum drying oven 60
DEG C vacuum bakeout 12h, obtained pole piece are anode.
Using metal lithium sheet as cathode.
Electrolyte are as follows: three pairs of methyl fluoride sulfonic acid Asia amide lithiums and LiNO3It is dissolved in the glycol dimethyl ether and 1 of volume ratio 1:1,
In the mixed liquor of 3 dioxolanes, wherein three pairs of methyl fluoride sulfonic acid Asia amide lithium concentrations are 1M, LiNO3Concentration is 0.2M.
It is fabricated to CR2032 button battery.
2, lithium-sulfur cell electric performance test
Under 25 DEG C of constant temperatures, battery performance test is carried out to battery obtained.Thus each embodiment preparation is measured
After the first discharge specific capacity of spherical positive material for lithium-sulfur battery with monodispersity, and test circulating battery 200 weeks
Capacity retention ratio.
3, test result
Table 3 be each embodiment preparation polarity lithium-sulphur cell positive electrode carry sulfur materials in sulphur mass percentage and by this just
The spherical positive material for lithium-sulfur battery first discharge specific capacity and battery for the monodispersity that battery obtained by the material of pole measures
200 weeks capacity retention ratio test results of circulation.
Fig. 1,2,3,4,5 are respectively monodispersity spherical shape lithium-sulfur cell anode prepared by embodiment 1,5,10,15,20
The stereoscan photograph of material, spherical shape positive material for lithium-sulfur battery prepared by the present invention is electric in scanning it can be seen from photo
Showed under sub- microscope as carbon nanotube or graphene film are interlaced be entangled with made of spheric granules, and each spheric granules
Between independent balling-up, mutually dispersion adhesion, have monodispersity.
Monodispersity spherical shape positive material for lithium-sulfur battery of the invention is for the first time it can be seen from the test result in table 2
Specific discharge capacity is higher, and cycle performance is excellent.
As can be seen from the above results, monodispersity spherical shape positive material for lithium-sulfur battery of the invention, can pass through adjusting
Raw material proportioning, which accurately controls, carries sulfur content；There is excellent conduction using the spherical structure that carbon nanotube or graphene go out as framework construction
Network；The addition of nano-metal-oxide or nitride isopolarity absorption additive allows to effectively adsorb more lithium sulfides, consolidates
Determine polysulfide and make independent balling-up between each spheric granules, mutually dispersion adhesion, there is monodispersity；Spheric granules structure
Stablize, is not broken up in electrode production process or dusting.Therefore sulphur of the invention is uniformly distributed in the monodisperse inside particle
Property spherical shape positive material for lithium-sulfur battery sulphur in battery charge and discharge process utilization rate with higher, circulating battery 200 weeks hold
It is high to measure conservation rate, battery electrical property is superior.
It should be noted that being used to help understand the present invention for the explanation of these embodiments, but do not constitute
Limitation of the invention.In addition, as long as technical characteristic involved in each embodiment of the present invention does not constitute punching each other
It is prominent to be combined with each other, for example adhesive in the above embodiments used one kind, and in other implementations of the invention
Listed various adhesives, which can be combined with each other, in example, in Tables 1 and 2 uses, and makes spherical lithium sulphur electricity obtained
Positive electrode spheric granules in electrode production process in pond is not broken up or dusting, improves the stability of spheric granules.
In addition, the transition metal oxide as polarity absorption additive is received as particle and transition metal nitride nanometer
Grain also can be combined with each other use, such as the transition metal oxide zinc oxide of nano particle, ferroso-ferric oxide, oxidation
Titanium, vanadic anhydride can be combined with each other use between aluminium oxide, such as zinc oxide and ferroso-ferric oxide, ferroso-ferric oxide and oxygen
Change combination or the zinc oxide, four oxidations of two kinds of nanometer pellets such as titanium, zinc oxide and aluminium oxide, vanadic anhydride and aluminium oxide
The combination of three kinds of transition oxide nanometer pellets such as three-iron and titanium oxide；Be also possible to zinc oxide, ferroso-ferric oxide, titanium oxide,
The combination of four kinds of oxidate nano pellets such as vanadic anhydride, naturally it is also possible to be the combination of five kinds of oxidate nano pellets.It crosses
Crossing metal nitride titanium nitride nano pellet and vanadium nitride nanometer pellet can be applied in combination, can also be by transition metal nitride
It is applied in combination between nanometer pellet and transition metal oxide nano pellet, such as zinc-oxide nano pellet and vanadium nitride nanometer
Material is applied in combination, naturally it is also possible to be other transition metal nitride nanometer pellets of the present invention and it is of the present invention its
It is applied in combination between its transition metal oxide nano pellet, combination can be two kinds of combination or two or more groups
It closes, can achieve dispersion effect, so that mutual exclusion between prepared sphere material particle, has monodispersity, does not agglomerate, nothing
It needs the later period to crush, sieving process, greatly improves the efficiency of electrode preparation, no longer rose is lifted here.
Embodiment listed by the present invention is section Example, rather than whole embodiments, based on listed in description of the invention
Embodiment out, those of ordinary skill in the art's every other implementation obtained without making creative work
Example, shall fall within the protection scope of the present invention.
The mass fraction of raw material used in 1 embodiment 1 to embodiment 10 of table and raw material
The mass fraction of raw material used in 2 embodiment 11 to embodiment 20 of table and raw material
Table 3
Claims (8)
1. it is a kind of spherical shape lithium sulfur battery anode material preparation method, which is characterized in that the preparation method is as follows: by sulphur presoma,
Carbon source, adhesive and polarity absorption additive are distributed in water, are spray-dried after mixing evenly, and monodispersity spherical shape lithium sulphur is made
Cell positive material.
2. the preparation method of spherical shape lithium sulfur battery anode material as described in claim 1, which is characterized in that the sulphur presoma
For ammonium polysulfide solution or thiosulfuric acid ammonium salt solution.
3. the preparation method of spherical shape lithium sulfur battery anode material as claimed in claim 1 or 2, which is characterized in that the carbon source
For at least one of carbon nano tube dispersion liquid or graphene dispersing solution, dispersion solvent is water, N-Methyl pyrrolidone, N, N-
One of dimethylformamide.
4. the preparation method of spherical shape lithium sulfur battery anode material as claimed in claim 1 or 2, which is characterized in that described to cohere
Agent is water-soluble polymer solution, and solute is polyacrylamide, polyvinylpyrrolidone, polyethylene glycol, polyethylene glycol oxide, water
Property polyurethane, kayexalate, poly- (3,4-rthylene dioxythiophene)-poly- (styrene sulfonate), phenolic resin, polydiene
In diallyidimethylammonium chloride, sodium alginate, sodium carboxymethylcellulose, chitosan, polylactic acid, xanthan gum or cluster bean at least
It is a kind of.
5. the preparation method of spherical shape lithium sulfur battery anode material as claimed in claim 1 or 2, which is characterized in that the polarity
Absorption additive is transition metal oxide nano particle or transition metal nitride nano particle.
6. the preparation method of spherical shape lithium sulfur battery anode material as claimed in claim 5, which is characterized in that the transition metal
Oxide is at least one of zinc oxide, ferroso-ferric oxide, titanium oxide, vanadic anhydride, aluminium oxide；Transition metal nitride
For at least one of titanium nitride, vanadium nitride.
7. the preparation method of spherical shape lithium sulfur battery anode material as claimed in claim 1 or 2, which is characterized in that described spraying
Drying temperature is 130~190 DEG C.
8. such as the spherical lithium sulfur battery anode material of one of claim 1 to 7 the method preparation, which is characterized in that the ball
Shape lithium sulfur battery anode material is made of sulphur, carbon carrier, polymeric additive and polarity absorption additive, the spherical shape lithium sulphur electricity
Sulphur is presented under a scanning electron microscope and is uniformly distributed in being entangled with by carbon nanotube is interlaced for inside for pond positive electrode
Monodispersity spheric granules or sulphur be uniformly distributed in it is internal as graphene film is interlaced be entangled with made of monodispersity ball
Shape particle.
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Cited By (5)
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|---|---|---|---|---|
| CN110718680A (en) * | 2019-10-22 | 2020-01-21 | 深圳中华自行车(集团)股份有限公司 | Lithium manganate battery positive plate and preparation method thereof |
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| CN113130219A (en) * | 2021-04-27 | 2021-07-16 | 刘大佐 | Nitrogen-sulfur co-doped porous carbon-coated mesoporous VN supercapacitor material and preparation method thereof |
| CN113130219B (en) * | 2021-04-27 | 2023-07-18 | 刘大佐 | Nitrogen-sulfur co-doped porous carbon coated mesoporous VN supercapacitor material and preparation method thereof |
| WO2024179533A1 (en) * | 2023-03-01 | 2024-09-06 | 郑州大学 | Aqueous binder and use thereof in hard carbon negative electrode of sodium-ion battery |
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