CN109698344A - A kind of preparation method of lithium sulfur battery anode material - Google Patents
A kind of preparation method of lithium sulfur battery anode material Download PDFInfo
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- CN109698344A CN109698344A CN201910040201.7A CN201910040201A CN109698344A CN 109698344 A CN109698344 A CN 109698344A CN 201910040201 A CN201910040201 A CN 201910040201A CN 109698344 A CN109698344 A CN 109698344A
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- H—ELECTRICITY
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
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- H—ELECTRICITY
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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- H—ELECTRICITY
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- H01M2004/021—Physical characteristics, e.g. porosity, surface area
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- H—ELECTRICITY
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a kind of preparation methods of lithium sulfur battery anode material, specific preparation process is as follows: appropriate zinc nitrate hexahydrate, phthalic acid, Ketjen black and surfactant are added to N, mixed solution is made in dinethylformamide, then mixed liquor is stirred by ultrasonic to being uniformly dispersed；Mixed liquor is fitted into progress hydro-thermal reaction in hydrothermal reaction kettle and obtains KB@MOF-5；KB@MOF-5 is placed in the tube furnace of inert gas shielding, KB@Meso-C is obtained after high temperature cabonization；In the tube furnace of inert gas shielding, by being heat-treated active sulfur heat fusing into KB@Meso-C composite material, KB@Meso-C/S is obtained.The present invention is by coating Ketjen black on the surface of positive electrode, the dissolution of the more lithium sulfides of the intermediate product in charge and discharge process of the active sulfur in lithium sulfur battery anode material and the shuttle in positive and negative interpolar back and forth can be effectively relieved, lithium sulfur battery anode material electronic conductivity and lithium ionic mobility are improved, to improve the reversible specific capacity of lithium-sulfur cell, high rate performance, cyclical stability and service life.
Description
Technical field
The invention belongs to lithium battery preparation fields, are related to a kind of preparation method of lithium sulfur battery anode material.
Background technique
The concept of lithium-sulfur cell is put forward for the first time in the 1960s, as promising next-generation lithium secondary battery body
System, lithium-sulfur cell is by the reversible electrochemical reaction storage between lithium and sulphur and to convey energy, theoretically, due to its activity
The theoretical capacity 1675mAh g of material sulphur-1An order of magnitude higher than conventional batteries, the energy density (2600Wh of lithium-sulfur cell
kg-1) commercial batteries are five times in, traditional anode material for lithium-ion batteries theoretical energy density is in 350~400Wh kg-1, practical
Energy density is in 100~220Wh kg-1, it is limited in application (such as electric car, static energy storage of high-power charge and discharge electrical domain
Deng), since conventional batteries lose its attraction in electric vehicle and portable device, lithium-sulfur cell is gradually popular.
The academic research of lithium-sulfur cell at present is not yet converted into business success, and poor cyclical stability is to hinder it
The main problem strided forward to application, there are the problem of mainly have the following:
(1) insulating properties of sulphur: elementary sulfur and its lithium compound (Li2S) non-conductive, that causes sulphur utilizes limited, seldom reality
Existing theoretical capacity.Therefore, in order to ensure high capacity and high rate performance, conducting base plays key effect.
(2) soluble polysulfide: long-chain lithium-sulphur compound (Li2Sx, x=4~8) dissolution lead to more sulphur near anode
Compound concentration is bigger than normal, diffuses out under concentration gradient driving from anode, leads to the reduction of capacity.During circulating battery,
Electrolysis fluid viscosity is gradually increased and is saturated, and the migration of polysulfide will be mitigated.
(3) shuttle effect: describe partly soluble polysulfide between two electrodes constantly shuttle and convert show
As leading to low coulombic efficiency, being the main reason for battery capacity reduces.However, it has been recently discovered that, the addition in electrolyte
Agent such as LiNO3Passivating film can be generated on cathode of lithium, this helps to inhibit surface reaction and shuttle effect.
(4) Morphology Remodeling: Gu since the electrochemical process in lithium-sulfur cell needs solid-liquid-transformation, duplicate nucleation and
Dissolution will generate significant influence to the form of electrode, and active material will redistribute in anode, and from conducting base
Those of isolating will become inactive, and volume expansion complicates redistribution, this causes positive form and its original state complete
It is complete different.
Summary of the invention
The purpose of the present invention is to provide a kind of preparation method of lithium sulfur battery anode material, this method passes through in positive material
The surface of material coats Ketjen black, and the intermediate production in charge and discharge process of the active sulfur in lithium sulfur battery anode material can be effectively relieved
The dissolution of the more lithium sulfides of object and shuttle in positive and negative interpolar back and forth improve lithium sulfur battery anode material electronic conductivity and lithium ion
Mobility, to improve the reversible specific capacity of lithium-sulfur cell, high rate performance, cyclical stability and service life.
The purpose of the present invention can be achieved through the following technical solutions:
A kind of preparation method of lithium sulfur battery anode material, specific preparation process are as follows:
Appropriate zinc nitrate hexahydrate, phthalic acid, Ketjen black and a certain amount of surfactant are added to foot by the first step
Mixed solution is made in the n,N-Dimethylformamide (DMF) of amount, then mixed liquor is stirred by ultrasonic to being uniformly dispersed；
Second step, after the resulting mixed liquor of the first step is fitted into hydrothermal reaction kettle hydro-thermal reaction for a period of time, by hydro-thermal
Reaction kettle is placed into baking oven be heated to set temperature after held for some time, room temperature is then naturally cooled to, then by hydro-thermal
It is dried after precipitating filtration washing in reaction kettle, obtains Ketjen black and coat metal organic frame MOF-5 composite material, i.e. KB@
MOF-5；
The resulting presoma KB@MOF-5 of second step is placed in the tube furnace of inert gas shielding, through height by third step
The coating mesoporous carbon composite of Ketjen black, i.e. KB@Meso-C are obtained after temperature carbonization；
4th step will be obtained by active sulfur heat fusing to third step as heat treatment in the tube furnace of inert gas shielding
It is final to obtain the coating mesoporous carbon of Ketjen black/sulphur composite material, i.e. KB@Meso-C/S in KB@Meso-C composite material.
Preferably, zinc nitrate hexahydrate and phthalic acid molar ratio are (1.5~3) in the first step: 1, Ketjen black and benzene diformazan
The mass ratio of acid is 1:3~6, and the mass ratio of surfactant and Ketjen black is 1:10~15.
Preferably, surfactant is polyethylene glycol, hydroxyethyl cellulose, poly amic acid, polyethylene pyrrole in the first step
One of pyrrolidone, polyoxyethylene analog copolymer or at least two combinations.
Preferably, ultrasonic power is 40~80KHz in the first step, and 15~60min of time is stirred by ultrasonic.
Preferably, baking oven heating rate is 3~5 DEG C in second step, and hydrothermal temperature is 105~140 DEG C, the reaction time
≥24h；Sediment KB MOF-5 washs filtering >=3 time with DMF, while the KB MOF-5 drying temperature of washed filtering is 150
~160 DEG C, baking time >=12h.
Preferably, protective gas is one of nitrogen, argon gas, helium, neon, shield gas flow rate 50 in third step
~80mL/min.
Preferably, tube furnace heating rate is 3~10 DEG C/min in third step, and high temperature cabonization temperature is 900~1000 DEG C,
Carbonization time is 3~5h.
Preferably, one of protective gas argon gas, helium, neon in the 4th step, shield gas flow rate are 30~50mL/
min；Tube furnace heating rate be 2~5 DEG C/min, while heat treatment temperature be 150~160 DEG C, heat treatment time be 10~
12h。
Preferably, the mass ratio of active sulfur and KB@Meso-C are 1.5~2:1 in the 4th step.
Beneficial effects of the present invention:
The surface of positive electrode prepared by the present invention coats Ketjen black, can be effectively relieved in lithium sulfur battery anode material
The dissolution of the more lithium sulfides of active sulfur intermediate product in charge and discharge process and shuttle in positive and negative interpolar back and forth improve lithium-sulfur cell
Positive electrode electronic conductivity and lithium ionic mobility, so that it is steady to improve the reversible specific capacity of lithium-sulfur cell, high rate performance, circulation
The qualitative and service life.
Detailed description of the invention
In order to facilitate the understanding of those skilled in the art, the present invention will be further described below with reference to the drawings.
Fig. 1 is the XRD curve graph of KB@Meso-C/S and simple substance S positive electrode prepared in embodiment 1.
It is the scanning electron microscope (SEM) photograph of lithium sulfur battery anode material KB@Meso-C/S in embodiment 1 in Fig. 2.
Fig. 3 is the cycle performance curve comparison figure of lithium sulfur battery anode material in embodiment 1 and comparative example 1.
Specific embodiment
Fig. 1-3 is please referred to be described in detail in conjunction with following examples:
Embodiment 1
A kind of preparation method of lithium sulfur battery anode material, specific preparation process are as follows:
The first step, by 1.78g Zn (NO3)2·6H2O、0.33g C8H6O4, 0.1g KB and 10mg polyethylene glycol be added
Into the DMF of 60mL, ultrasonic power is set as 60KHz, forms evenly dispersed mixed liquor after 30min is stirred by ultrasonic；
The mixed liquor of first step preparation is added hydrothermal reaction kettle and is placed in baking oven, with the heating of 5 DEG C/min by second step
Rate is warming up to 135 DEG C of heat preservations and naturally cools to room temperature afterwards for 24 hours, and sediment is washed filtering with DMF and is placed on 150 DEG C three times very
It is kept the temperature in empty baking oven and obtains precursor complex KB@MOF-5 afterwards for 24 hours；
Precursor complex KB@MOF-5 obtained by second step is placed in the tube furnace of nitrogen atmosphere, nitrogen gas by third step
Body flow is 60mL/min, after being heated to 900 DEG C of heat preservation 3h with the heating rate of 5 DEG C/min, cools to room temperature with the furnace and obtains KB@
Meso-C composite material；
The resulting KB@Meso-C composite material of third step with active sulfur is that 7:13 is uniformly mixed by the 4th step in mass ratio
It is placed into the tube furnace of argon gas protection afterwards and is heated to keep the temperature 10h, furnace cooling after 155 DEG C with the heating rate of 2 DEG C/min
KB@Meso-C/S composite positive pole is obtained after to room temperature.
Embodiment 2
A kind of preparation method of lithium sulfur battery anode material, specific preparation process are as follows:
The first step, 1.19g Zn (NO3)2·6H2O、0.33g C8H6O4, 0.07g KB and 6mg poly amic acid be added
Into the DMF of 50mL, ultrasonic power is set as 50KHz, forms evenly dispersed mixed liquor after 35min is stirred by ultrasonic；
The mixed liquor of first step preparation is added hydrothermal reaction kettle and is placed in baking oven, with the heating of 3 DEG C/min by second step
Rate is warming up to 110 DEG C of heat preservations and naturally cools to room temperature afterwards for 24 hours, and sediment is washed filtering with DMF and is placed on 155 DEG C three times very
Precursor complex KB@MOF-5 is obtained after keeping the temperature 16h in empty baking oven；
Precursor complex KB@MOF-5 obtained by second step is placed in the tube furnace of nitrogen atmosphere, nitrogen gas by third step
Body flow is 50mL/min, after being heated to 950 DEG C of heat preservation 5h with the heating rate of 10 DEG C/min, cools to room temperature acquisition with the furnace
KB@Meso-C composite material.
4th step, by the resulting KB@Meso-C composite material of third step and active sulfur be in mass ratio 1:2 after evenly mixing
It is placed into after being heated to 155 DEG C in the tube furnace of argon gas protection with the heating rate of 3 DEG C/min and keeps the temperature 12h, cool to the furnace
KB@Meso-C/S composite positive pole is obtained after room temperature.
Embodiment 3
A kind of preparation method of lithium sulfur battery anode material, specific preparation process are as follows:
The first step, 1.49g Zn (NO3)2·6H2O、0.33g C8H6O4, 0.08g KB and 8mg hydroxyethyl cellulose adds
Enter into the DMF of 60mL, sets ultrasonic power as 70KHz, form evenly dispersed mixed liquor after 40min is stirred by ultrasonic；
The mixed liquor of first step preparation is added hydrothermal reaction kettle and is placed in baking oven, with the heating of 5 DEG C/min by second step
Rate is warming up to 140 DEG C of heat preservations and naturally cools to room temperature afterwards for 24 hours, and sediment is washed filtering with DMF and is placed on 160 DEG C three times very
Precursor complex KB@MOF-5 is obtained after keeping the temperature 12h in empty baking oven；
Precursor complex KB@MOF-5 obtained by second step is placed in the tube furnace of nitrogen atmosphere, nitrogen gas by third step
Body flow is 70mL/min, after being heated to 1000 DEG C of heat preservation 4h with the heating rate of 10 DEG C/min, cools to room temperature acquisition with the furnace
KB@Meso-C composite material；
4th step, by the resulting KB@Meso-C composite material of third step and active sulfur be in mass ratio 2:3 after evenly mixing
It is placed into after being heated to 155 DEG C in the tube furnace of argon gas protection with the heating rate of 5 DEG C/min and keeps the temperature 10h, cool to the furnace
KB@Meso-C/S composite positive pole is obtained after room temperature.
Comparative example 1
A kind of preparation method of lithium sulfur battery anode material, specific preparation process are as follows:
The first step, 1.78g Zn (NO3)2·6H2O、0.33g C8H6O4And 10mg polyethylene glycol is added to the DMF of 60mL
In, ultrasonic power is set as 60KHz, forms evenly dispersed mixed liquor after 30min is stirred by ultrasonic；
The mixed liquor of first step preparation is added hydrothermal reaction kettle and is placed in baking oven, with the heating of 5 DEG C/min by second step
Rate is warming up to 135 DEG C of heat preservations and naturally cools to room temperature afterwards for 24 hours, and sediment is washed filtering with DMF and is placed on 150 DEG C three times very
It is kept the temperature in empty baking oven and obtains precursor complex MOF-5 afterwards for 24 hours；
Precursor complex MOF-5 obtained by second step is placed in the tube furnace of nitrogen atmosphere, nitrogen gas stream by third step
Amount is 60mL/min, after being heated to 900 DEG C of heat preservation 3h with the heating rate of 5 DEG C/min, cools to room temperature with the furnace and obtains Meso-C
Composite material；
The resulting Meso-C composite material of third step with active sulfur is that 7:13 is put after evenly mixing by the 4th step in mass ratio
It sets and keeps the temperature 10h after being heated to 155 DEG C in the tube furnace of argon gas protection with the heating rate of 2 DEG C/min, cool to room with the furnace
Meso-C/S composite positive pole is obtained after temperature.
As shown in Figure 1, active sulfur is successfully coated in positive electrode, while from the figure 3, it may be seen that embodiment 1 positive material
The lithium battery first discharge specific capacity of material preparation reaches 998mAh g-1, and use comparative example 1 in positive electrode preparation lithium from
Sub- battery discharge specific capacity is only 686mAh g-1, while the lithium ion battery of the positive electrode preparation of embodiment 1 passes through 300 times
Specific discharge capacity remains to reach 665mAh g after recycling-1, and the lithium ion battery of the positive electrode of comparative example 1 preparation passes through
Specific discharge capacity is only 360mAh g after 300 circulations-1, since the positive electrode surface prepared in embodiment 1 passes through Ketjen black
Cladding, and then the dissolution of active sulfur and the shuttle in positive and negative interpolar back and forth are alleviated, while Ketjen black is with higher corrosion-resistant
Performance makes so that coating the positive electrode alleviation performance still with higher of Ketjen black under the corrosion function of electrolyte
Its cycle performance is obtained to improve.
Present invention disclosed above preferred embodiment is only intended to help to illustrate the present invention.There is no detailed for preferred embodiment
All details are described, are not limited the invention to the specific embodiments described.Obviously, according to the content of this specification,
It can make many modifications and variations.These embodiments are chosen and specifically described to this specification, is in order to better explain the present invention
Principle and practical application, so that skilled artisan be enable to better understand and utilize the present invention.The present invention is only
It is limited by claims and its full scope and equivalent.
Claims (9)
1. a kind of preparation method of lithium sulfur battery anode material, which is characterized in that specific preparation process is as follows:
Appropriate zinc nitrate hexahydrate, phthalic acid, Ketjen black and a certain amount of surfactant are added to enough by the first step
Mixed solution is made in n,N-Dimethylformamide, then mixed liquor is stirred by ultrasonic to being uniformly dispersed；
Second step, after the resulting mixed liquor of the first step is fitted into hydrothermal reaction kettle hydro-thermal reaction for a period of time, by hydro-thermal reaction
Kettle is placed into baking oven be heated to set temperature after held for some time, room temperature is then naturally cooled to, then by hydro-thermal reaction
It is dried after precipitating filtration washing in kettle, obtains Ketjen black and coat metal organic frame MOF-5 composite material, i.e. KB@MOF-5；
The resulting presoma KB@MOF-5 of second step is placed in the tube furnace of inert gas shielding, through pyrocarbon by third step
The coating mesoporous carbon composite of Ketjen black, i.e. KB@Meso-C are obtained after change；
4th step, in the tube furnace of inert gas shielding, as being heat-treated KB@obtained by active sulfur heat fusing to third step
It is final to obtain the coating mesoporous carbon of Ketjen black/sulphur composite material, i.e. KB@Meso-C/S in Meso-C composite material.
2. a kind of preparation method of lithium sulfur battery anode material according to claim 1, which is characterized in that six in the first step
Water zinc nitrate and phthalic acid molar ratio are (1.5~3): 1, the mass ratio of Ketjen black and phthalic acid is 1:3~6, and surface is living
Property agent and Ketjen black mass ratio be 1:10~15.
3. a kind of preparation method of lithium sulfur battery anode material according to claim 1, which is characterized in that table in the first step
Face activating agent is polyethylene glycol, in hydroxyethyl cellulose, poly amic acid, polyvinylpyrrolidone, polyoxyethylene analog copolymer
One kind or at least two combination.
4. a kind of preparation method of lithium sulfur battery anode material according to claim 1, which is characterized in that surpass in the first step
Acoustical power is 40~80KHz, and 15~60min of time is stirred by ultrasonic.
5. a kind of preparation method of lithium sulfur battery anode material according to claim 1, which is characterized in that dried in second step
Case heating rate is 3~5 DEG C, and hydrothermal temperature is 105~140 DEG C, the reaction time >=for 24 hours；Sediment KB@MOF-5 DMF
Washing filtering >=3 times, while the KB MOF-5 drying temperature of washed filtering is 150~160 DEG C, baking time >=12h.
6. a kind of preparation method of lithium sulfur battery anode material according to claim 1, which is characterized in that protected in third step
Shield gas is one of nitrogen, argon gas, helium, neon, and shield gas flow rate is 50~80mL/min.
7. a kind of preparation method of lithium sulfur battery anode material according to claim 1, which is characterized in that managed in third step
Formula furnace heating rate is 3~10 DEG C/min, and high temperature cabonization temperature is 900~1000 DEG C, and carbonization time is 3~5h.
8. a kind of preparation method of lithium sulfur battery anode material according to claim 1, which is characterized in that protected in the 4th step
One of gases argon, helium, neon are protected, shield gas flow rate is 30~50mL/min；Tube furnace heating rate is 2~5
DEG C/min, while heat treatment temperature is 150~160 DEG C, heat treatment time is 10~12h.
9. a kind of preparation method of lithium sulfur battery anode material according to claim 1, which is characterized in that living in the 4th step
Property sulphur and KB@Meso-C mass ratio be 1.5~2:1.
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Application publication date: 20190430 |