CN109346678A - A kind of high-sulfur load lithium-sulphur cell positive electrode and preparation method thereof, lithium-sulfur cell - Google Patents
A kind of high-sulfur load lithium-sulphur cell positive electrode and preparation method thereof, lithium-sulfur cell Download PDFInfo
- Publication number
- CN109346678A CN109346678A CN201811390629.6A CN201811390629A CN109346678A CN 109346678 A CN109346678 A CN 109346678A CN 201811390629 A CN201811390629 A CN 201811390629A CN 109346678 A CN109346678 A CN 109346678A
- Authority
- CN
- China
- Prior art keywords
- sulphur
- lithium
- positive electrode
- carbon
- sulfur
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/0402—Methods of deposition of the material
- H01M4/0404—Methods of deposition of the material by coating on electrode collectors
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
-
- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The present invention provides a kind of preparation methods of high-sulfur load lithium-sulphur cell positive electrode, comprising the following steps: is added to the water carbon material and sulphur, is uniformly mixed and obtains carbon sulphur mixed serum；Carbon sulphur mixed serum is added in sand mill and carries out nano ball grinding, then is dried and crushes, then heating melting, obtains carbon sulphur composite positive pole；Conductive agent, adhesive and carbon sulphur composite positive pole are added to the water, lithium-sulphur cell positive electrode slurry presoma is made after mixing, then anode sizing agent presoma is added in sand mill and carries out nano ball grinding, obtains lithium-sulphur cell positive electrode slurry；Lithium-sulphur cell positive electrode slurry is coated uniformly on aluminium foil, obtains high-sulfur load lithium-sulphur cell positive electrode after drying.This method cost of material is low, simple process, process control, is conducive to that the high lithium-sulphur cell positive electrode of sulphur load capacity is made.The present invention correspondingly provides lithium-sulphur cell positive electrode obtained by this method, and assembles obtained lithium-sulfur cell by the anode.
Description
Technical field
The invention belongs to technical field of lithium ion more particularly to a kind of high-sulfur load lithium-sulphur cell positive electrode and its preparations
Method, lithium-sulfur cell.
Background technique
According to national planning, in nearly 30 years can the specific capacities of lithium battery of charge and discharge to reach energy density 400Wh/kg
More than.But it is limited by traditional positive electrode such as cobalt acid lithium, LiFePO4 scheduling theory specific capacity, traditional lithium ion battery energy
Density is difficult to be increased to 300Wh/kg or more, thus needs to develop new lithium battery system to reach 400Wh/kg or more.Lithium sulphur
Battery be it is generally acknowledged in the world at present being capable of commercial applications and energy density can reach 400Wh/kg or more in a short time
Novel lithium battery.But this battery want practical application there are also many problems to need to solve, such as anode in sulphur insulation
Property, the shuttle effect of soluble polysulfide in electrolyte, cathode Li dendrite growth the problems such as.From raising lithium-sulfur cell energy
From the point of view of density, needs most and solve the problems, such as to be exactly to improve the load capacity of sulphur and the benefit of active material sulphur in anode pole piece
With rate.
Using conventional method will active material, conductive agent and adhesive simple agitation mix after be difficult to coat out high-sulfur and bear
The pole piece of load, the load capacity for the sulphur that most of document so far is recorded is all in 1mg/cm2Left and right；Although these lithium-sulfur cells
The specific capacity of report is relatively high, but the actually capacity that is capable of providing of unit area is smaller, and the requirement of application is not achieved.And
Although small part lithium-sulphur cell positive electrode sulphur load capacity reported in the literature is high, preparation process is more complicated, is unfavorable for the expansion of production
Bigization.As Chinese patent application CN201410208703.3 discloses a kind of lithium-sulfur cell flexibility high-sulfur load selfreparing anode knot
Structure and preparation method thereof improves the load of sulphur mainly using graphene/polymer polymer flexibility foam as the carrier of sulphur
Amount；This method first has to prepare qualified graphene/polymer polymer flexibility foam, and sulphur is then penetrated into carrier again
In, on the one hand the preparation difficulty of this flexible foam is higher, and on the other hand, the infiltration technical difficulty of sulphur is also bigger, Ke Nengzao
At the uneven of sulphur content cloth, it is unfavorable for expanding production.
Summary of the invention
The technical problem to be solved by the present invention is to overcome the shortcomings of to mention in background above technology and defect, provide one
Kind high-sulfur load lithium-sulphur cell positive electrode and preparation method thereof, lithium-sulfur cell.
In order to solve the above technical problems, technical solution proposed by the present invention are as follows:
A kind of preparation method of high-sulfur load lithium-sulphur cell positive electrode, comprising the following steps:
(1) carbon material and sulphur are added to the water, are uniformly mixed and obtain carbon sulphur mixed serum；
(2) the carbon sulphur mixed serum after step (1) is added in sand mill and carries out nano ball grinding, then simultaneously powder is dried
Broken, then heating melting, penetrates into sulphur in the duct of carbon material, obtains carbon sulphur composite positive pole；
(3) the carbon sulphur composite positive pole after conductive agent, adhesive and step (2) is added to the water, is made after mixing
Lithium-sulphur cell positive electrode slurry presoma is obtained, then anode sizing agent presoma is added in sand mill and carries out nano ball grinding, obtains lithium
Sulphur cell positive electrode slurry；
(4) the lithium-sulphur cell positive electrode slurry after step (3) is coated uniformly on aluminium foil, obtains high-sulfur load after drying
Lithium-sulphur cell positive electrode.
Preparation method of the invention is set using sand milling during preparing carbon sulphur composite positive pole and anode sizing agent
It is standby, nano ball grinding is carried out by the way that carbon sulphur mixed serum to be added in sand mill first, the granularity of sulphur is made to reach nanoscale, and and carbon
Particle is sufficiently mixed, and realizes sulphur in the uniform cladding of carbon surface, to promote sulphur equably to penetrate into carbon during heating melting
In duct, while it ensure that the infiltration capacity of sulphur；Nano ball grinding is carried out by the way that anode sizing agent presoma to be added in sand mill again, is made
Active material is uniformly dispersed in anode sizing agent, does not generate reunion, to be conducive to the transmission of lithium ion, improves the electricity of anode
Chemical property.
Above-mentioned preparation method, it is preferred that in the step (2) and step (3), the revolving speed of nano ball grinding is 1000-
1500rpm, time 20-60min.Preparation method of the invention, within the scope of the invention by the state modulator of nano ball grinding,
It can guarantee that material is uniformly mixed, while the structure of material will not be destroyed.
Above-mentioned preparation method, it is preferred that carbon material is Ketjen black, carbon nanotube, Cabot conduction in the step (1)
One or more of carbon black BP2000, acetylene black, graphene；The mass ratio of the carbon material and sulphur is 1:(2-9)；The carbon
The solid content of sulphur mixed serum is 10%-30%.Preparation method of the invention, preferred carbon material have the characteristics that duct is more,
It is easy to sulfurizing；Within the scope of the invention by the control of the mass ratio of carbon material and sulphur, be conducive to be promoted the specific capacity of anode；By carbon
The solid content control of sulphur mixed serum within the scope of the invention, is conducive to crush particle for nanoscale simultaneously in process of lapping
Guarantee that sulphur is evenly coated in carbon surface.Above-mentioned preparation method, it is preferred that in the step (3) conductive agent be carbon nanotube,
One or more of Super-P, acetylene black；Described adhesive is aqueous binder, specially sodium carboxymethylcellulose and fourth
Mixture (CMC/SBR), the acrylonitrile multiple copolymer (La133 or La132), polytetrafluoroethylene (PTFE) (PTFE), seaweed of benzene rubber
One or more of sour sodium.
Above-mentioned preparation method, it is preferred that drying carries out in air dry oven in the step (2), controlled at
45-80 DEG C, time 10-24h；Described be melted in vacuum drying oven carries out, controlled at 155-200 DEG C, time 10-
24h.Within the scope of the invention by drying parameter and fusion parameters control, can volatilize to avoid sulphur leads to active material loss
Phenomenon is conducive to sulphur and is fully infiltrated into the duct of carbon material, while the phenomenon that powder can also be avoided to reunite.
Above-mentioned preparation method, it is preferred that carbon sulphur composite positive pole in the step (3), conductive agent and adhesive
Mass ratio is (6-8): (3-1): 1；The solid content of the lithium-sulphur cell positive electrode slurry is 10%-30%,.By carbon sulphur anode composite
The mass ratio control of material, conductive agent and adhesive three within the scope of the invention, is conducive to the synthesis for promoting anode composite
Performance, if beyond the scope of this invention, the amount of active material is reduced, and will affect the energy density of compound rear anode, if low
In the scope of the present invention, the decline of positive plate bonding force will lead to；The solid content of lithium-sulphur cell positive electrode slurry is controlled in the present invention
In the range of, be conducive to the coating of pole piece, if beyond the scope of this invention, slurry is too thick, it will lead to and be unevenly coated, if
Lower than the scope of the present invention, slurry is too dilute, will be not easy drying.
Above-mentioned preparation method, it is preferred that in the step (4), in order to guarantee the amount of active material in anode, when coating
The height of scraper is 200-500um, and the drying carries out in air dry oven, and control drying temperature is 60-100 DEG C, drying
Time is 1-6h.When drying temperature or drying time are lower than the scope of the present invention, will lead to moisture in anode cannot steam completely
Hair；When beyond the scope of this invention, positive cracking will lead to.
The inventive concept total as one, the present invention also provides a kind of high-sulfur loads that above-mentioned preparation method is prepared
Lithium-sulphur cell positive electrode, sulphur load capacity is 3-10mg/cm in the lithium-sulphur cell positive electrode2。
The inventive concept total as one, the present invention also provides a kind of lithium-sulfur cells, load lithium sulphur including above-mentioned high-sulfur
Anode, cathode and electrolyte.
Above-mentioned lithium-sulfur cell, it is preferred that the electrolyte is bis trifluoromethyl sulfonic acid Asia amide lithium, lithium nitrate, 1,3-
The mixed solution of dioxolanes and glycol dimethyl ether, the cathode are metal lithium sheet.
Compared with the prior art, the advantages of the present invention are as follows:
(1) preparation method of the invention carries out nano ball grinding and heating melting to carbon sulphur mixed serum using sand mill
Mode prepare carbon sulphur composite positive pole, with it is common be stirred method and chemical method compared with, enhance sulphur in carbon substrate
The uniformity being distributed in material enables sulphur after heating melting to be distributed more evenly across in the duct of carbon material, is conducive to sulphur ratio
The performance of capacity.
(2) preparation method of the invention carries out nano ball grinding to lithium-sulphur cell positive electrode slurry presoma using sand mill, has
Conducive to the dispersion of sulphur, the uniformity of slurry is enhanced, and improves the coating quality of slurry, higher thickness can be coated with
Degree obtains high-sulfur load lithium-sulphur cell positive electrode.
(3) preparation method of the invention replaces common PVDF oil binder by using aqueous binder, reduces
Preparation cost reduces the environmental pollution in preparation process.
(4) preparation method of the invention uses sand during preparing carbon sulphur composite positive pole and anode sizing agent
Equipment is ground, can realize seamless interfacing with existing lithium ion battery production equipment, and is used compared to common be stirred
Time is shorter, improves material preparation efficiency.
(5) preparation method of the invention, cost of material is low, simple process, process control, is conducive to large-scale production, symbol
Close the requirement of commercial applications.
(6) the sulphur load capacity for the lithium-sulphur cell positive electrode being prepared by method of the invention is high, the lithium sulphur electricity assembled
Pond power is high, capacity is high, the service life is long, has great application prospect.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technical description to be briefly described, it should be apparent that, the accompanying drawings in the following description is the present invention
Some embodiments for those of ordinary skill in the art without creative efforts, can also basis
These attached drawings obtain other attached drawings.
Fig. 1 is the process flow diagram of the preparation method of high-sulfur load lithium-sulphur cell positive electrode in the embodiment of the present invention 1；
Fig. 2 is the schematic diagram of internal structure of the lithium-sulfur cell assembled in the embodiment of the present invention 1；
Fig. 3 is the cycle performance curve graph of the lithium-sulfur cell that assembles in the embodiment of the present invention 1 at 1C.
Specific embodiment
To facilitate the understanding of the present invention, invention herein is done below in conjunction with Figure of description and preferred embodiment more complete
Face meticulously describes, but protection scope of the present invention is not limited to following specific embodiments.
Unless otherwise defined, all technical terms used hereinafter are generally understood meaning phase with those skilled in the art
Together.Technical term used herein is intended merely to the purpose of description specific embodiment, and it is of the invention to be not intended to limitation
Protection scope.
Unless otherwise specified, various raw material, reagent, the instrument and equipment etc. used in the present invention can pass through city
Field is commercially available or can be prepared by existing method.
Embodiment 1:
A kind of preparation method of high-sulfur load lithium-sulphur cell positive electrode of the invention, process flow diagram as shown in Figure 1,
The following steps are included:
(1) 100g Ketjen black and 500g sulphur are added in 2.4kg pure water, are uniformly mixed and obtain carbon sulphur mixed serum,
Then carbon sulphur mixed serum is added in the barrel of sand mill and carries out nano ball grinding, rotational speed of ball-mill 1000rpm, Ball-milling Time is
30min；
(2) the carbon sulphur mixed serum after step (1) is dried 20 hours at 80 DEG C in air dry oven, carries out powder
It is broken, it is then transferred into vacuum drying oven, heat fusing 12 hours at 155 DEG C obtain Ketjen black/sulphur composite positive pole；
(3) by the Ketjen black after step (2)/sulphur composite positive pole, carbon nanotube, La133 type adhesive according to quality
Than being added to the water for 7:2:1, lithium-sulphur cell positive electrode slurry presoma is made after mixing, then adds anode sizing agent presoma
Enter and carry out nano ball grinding in the barrel of sand mill, rotational speed of ball-mill 1500rpm, the time is 30 minutes, and obtaining solid content is 15%
Lithium-sulphur cell positive electrode slurry；
(4) the lithium-sulphur cell positive electrode slurry after step (3) being coated uniformly on aluminium foil, blade thickness is set as 250um,
It is dried in air dry oven immediately after, drying temperature is 80 DEG C, and the time is 4 hours, and high-sulfur load is obtained after drying
Lithium-sulphur cell positive electrode.
In the present embodiment, the load capacity of sulphur is 3.3mg/cm in the lithium-sulphur cell positive electrode that is prepared2.It will be in the present embodiment
The high-sulfur load lithium-sulphur cell positive electrode and cathode, electrolyte being prepared are assembled into lithium-sulfur cell, and wherein cathode is metal lithium sheet,
Electrolyte is the mixed solution of bis trifluoromethyl sulfonic acid Asia amide lithium, lithium nitrate, 1,3- dioxolanes and glycol dimethyl ether；Shape
At lithium-sulfur cell schematic diagram of internal structure it is as shown in Figure 2.The lithium-sulfur cell being prepared is subjected to cycle performance test, is surveyed
For test result as shown in figure 3, it can be seen from the figure that activating for the first time under 0.1C, specific discharge capacity reaches 1200mAh/g, head under 1C
Secondary specific discharge capacity is 900mAh/g, and the specific discharge capacity of battery is 700mAh/g after recycling 100 times under 1C, and coulombic efficiency is greater than
97%.
Embodiment 2:
A kind of preparation method of high-sulfur load lithium-sulphur cell positive electrode of the invention, comprising the following steps:
(1) 100g carbon nanotube and 500g sulphur are added in 1.8kg pure water, are uniformly mixed and obtain carbon sulphur mixing slurry
Then carbon sulphur mixed serum is added in the barrel of sand mill and carries out nano ball grinding by liquid, rotational speed of ball-mill 1100rpm, when ball milling
Between be 20min；
(2) the carbon sulphur mixed serum after step (1) is dried 15 hours at 90 DEG C in air dry oven, carries out powder
It is broken, it is then transferred into vacuum drying oven, heat fusing 10 hours at 165 DEG C obtain carbon nanotube/sulphur composite positive pole；
(3) by the carbon nanotube after step (2)/sulphur composite positive pole, SuperP, La133 type adhesive according to quality
Than being added to the water for 7:2:1, lithium-sulphur cell positive electrode slurry presoma is made after mixing, then adds anode sizing agent presoma
Enter and carry out nano ball grinding in the barrel of sand mill, rotational speed of ball-mill 1300rpm, the time is 40 minutes, and obtaining solid content is 25%
Lithium-sulphur cell positive electrode slurry；
(4) the lithium-sulphur cell positive electrode slurry after step (3) being coated uniformly on aluminium foil, blade thickness is set as 240um,
It is dried in air dry oven immediately after, drying temperature is 70 DEG C, and the time is 6 hours, and high-sulfur load is obtained after drying
Lithium-sulphur cell positive electrode.
In the present embodiment, the load capacity of sulphur is 3.2mg/cm in the lithium-sulphur cell positive electrode that is prepared2.It will be in the present embodiment
The high-sulfur load lithium-sulphur cell positive electrode and cathode, electrolyte being prepared are assembled into lithium-sulfur cell, and wherein cathode is metal lithium sheet,
Electrolyte is the mixed solution of bis trifluoromethyl sulfonic acid Asia amide lithium, lithium nitrate, 1,3- dioxolanes and glycol dimethyl ether.It will
The lithium-sulfur cell being prepared carries out cycle performance test, activates for the first time under 0.1C, specific discharge capacity reaches 1150mAh/g, 1C
Lower first discharge specific capacity is 800mAh/g, and the specific discharge capacity of battery is 680mAh/g, coulombic efficiency after recycling 100 times under 1C
Greater than 97%.
Embodiment 3:
A kind of preparation method of high-sulfur load lithium-sulphur cell positive electrode of the invention, comprising the following steps:
(1) 80g Ketjen black, 20g carbon nanotube and 500g sulphur are added in 2kg pure water, are uniformly mixed and obtain carbon sulphur
Then carbon sulphur mixed serum is added in the barrel of sand mill and carries out nano ball grinding by mixed serum, rotational speed of ball-mill 1200rpm,
Ball-milling Time is 40min；
(2) the carbon sulphur mixed serum after step (1) is dried 20 hours at 60 DEG C in air dry oven, carries out powder
It is broken, it is then transferred into vacuum drying oven, heat fusing 10 hours at 160 DEG C obtain Ketjen black-carbon nanotube/sulphur anode composite
Material；
(3) by Ketjen black-carbon nanotube/sulphur composite positive pole, carbon nanotube, the La132 type adhesive after step (2)
It is added to the water according to mass ratio for 6:3:1, lithium-sulphur cell positive electrode slurry presoma is made after mixing, then by anode sizing agent
Presoma, which is added in the barrel of sand mill, carries out nano ball grinding, rotational speed of ball-mill 1000rpm, and the time is 50 minutes, admittedly contained
The lithium-sulphur cell positive electrode slurry that amount is 25%；
(4) the lithium-sulphur cell positive electrode slurry after step (3) being coated uniformly on aluminium foil, blade thickness is set as 300um,
It is dried in air dry oven immediately after, drying temperature is 100 DEG C, and the time is 1 hour, and high-sulfur load is obtained after drying
Lithium-sulphur cell positive electrode.
In the present embodiment, the load capacity of sulphur is 5.8mg/cm in the lithium-sulphur cell positive electrode that is prepared2.It will be in the present embodiment
The high-sulfur load lithium-sulphur cell positive electrode and cathode, electrolyte being prepared are assembled into lithium-sulfur cell, and wherein cathode is metal lithium sheet,
Electrolyte is the mixed solution of bis trifluoromethyl sulfonic acid Asia amide lithium, lithium nitrate, 1,3- dioxolanes and glycol dimethyl ether.It will
The lithium-sulfur cell being prepared carries out cycle performance test, activates for the first time under 0.1C, specific discharge capacity reaches 1000mAh/g, 1C
Lower first discharge specific capacity is 730mAh/g, and the specific discharge capacity of battery is 550mAh/g, coulombic efficiency after recycling 100 times under 1C
Greater than 97%.
Embodiment 4:
A kind of preparation method of high-sulfur load lithium-sulphur cell positive electrode of the invention, comprising the following steps:
(1) 80g BP2000 and 400g sulphur is added in 1.8kg pure water, is uniformly mixed and obtains carbon sulphur mixed serum,
Then carbon sulphur mixed serum is added in the barrel of sand mill and carries out nano ball grinding, rotational speed of ball-mill 1300rpm, Ball-milling Time is
60min；
(2) the carbon sulphur mixed serum after step (1) is dried 15 hours at 60 DEG C in air dry oven, carries out powder
It is broken, it is then transferred into vacuum drying oven, heat fusing 10 hours at 155 DEG C obtain BP2000/ sulphur composite positive pole；
(3) by after step (2) BP2000/ sulphur composite positive pole, acetylene black, CMC/SBR according to mass ratio be 8:1:1
It is added to the water, lithium-sulphur cell positive electrode slurry presoma is made after mixing, sand mill then is added in anode sizing agent presoma
Barrel in carry out nano ball grinding, rotational speed of ball-mill 1400rpm, the time is 30 minutes, obtains the lithium sulphur electricity that solid content is 20%
Pond anode sizing agent；
(4) the lithium-sulphur cell positive electrode slurry after step (3) being coated uniformly on aluminium foil, blade thickness is set as 350um,
It is dried in air dry oven immediately after, drying temperature is 80 DEG C, and the time is 5 hours, and high-sulfur load is obtained after drying
Lithium-sulphur cell positive electrode.
In the present embodiment, the load capacity of sulphur is 7mg/cm in the lithium-sulphur cell positive electrode that is prepared2.It will be made in the present embodiment
Standby obtained high-sulfur load lithium-sulphur cell positive electrode and cathode, electrolyte are assembled into lithium-sulfur cell, and wherein cathode is metal lithium sheet, electricity
Solution liquid is the mixed solution of bis trifluoromethyl sulfonic acid Asia amide lithium, lithium nitrate, 1,3- dioxolanes and glycol dimethyl ether.It will system
Standby obtained lithium-sulfur cell carries out cycle performance test, activates for the first time under 0.1C, and specific discharge capacity reaches 1010mAh/g, under 1C
First discharge specific capacity is 710mAh/g, and the specific discharge capacity of battery is 570mAh/g after recycling 100 times under 1C, and coulombic efficiency is big
In 97%.
Embodiment 5:
A kind of preparation method of high-sulfur load lithium-sulphur cell positive electrode of the invention, comprising the following steps:
(1) 70g acetylene black, 30g graphene and 800g sulphur are added in 4kg pure water, the uniformly mixed carbon sulphur that obtains mixes
Slurries are closed, then carbon sulphur mixed serum is added in the barrel of sand mill and carries out nano ball grinding, rotational speed of ball-mill 1400rpm, ball
Time consuming is 60min；
(2) the carbon sulphur mixed serum after step (1) is dried 18 hours at 80 DEG C in air dry oven, carries out powder
It is broken, it is then transferred into vacuum drying oven, heat fusing 10 hours at 175 DEG C obtain acetylene black-graphene/sulfur composite positive electrode material
Material；
(3) it is according to mass ratio by the acetylene black after step (2)-graphene/sulfur composite positive electrode material, SuperP, PTFE
7:2:1 is added to the water, and lithium-sulphur cell positive electrode slurry presoma is made after mixing, and sand then is added in anode sizing agent presoma
Nano ball grinding, rotational speed of ball-mill 1500rpm are carried out in the barrel of grinding machine, the time is 40 minutes, obtains the lithium that solid content is 18%
Sulphur cell positive electrode slurry；
(4) the lithium-sulphur cell positive electrode slurry after step (3) being coated uniformly on aluminium foil, blade thickness is set as 400um,
It is dried in air dry oven immediately after, drying temperature is 90 DEG C, and the time is 2 hours, and high-sulfur load is obtained after drying
Lithium-sulphur cell positive electrode.
In the present embodiment, the load capacity of sulphur is 8.1mg/cm in the lithium-sulphur cell positive electrode that is prepared2.It will be in the present embodiment
The high-sulfur load lithium-sulphur cell positive electrode and cathode, electrolyte being prepared are assembled into lithium-sulfur cell, and wherein cathode is metal lithium sheet,
Electrolyte is the mixed solution of bis trifluoromethyl sulfonic acid Asia amide lithium, lithium nitrate, 1,3- dioxolanes and glycol dimethyl ether.It will
The lithium-sulfur cell that is prepared carries out cycle performance test, activates for the first time under 0.1C, and specific discharge capacity reaches 990mAh/g, under 1C
First discharge specific capacity is 800mAh/g, and the specific discharge capacity of battery is 550mAh/g after recycling 100 times under 1C, and coulombic efficiency is big
In 97%.
Embodiment 6:
A kind of preparation method of high-sulfur load lithium-sulphur cell positive electrode of the invention, comprising the following steps:
(1) 60g Ketjen black, 20g graphene and 600g sulphur are added in 3kg pure water, the uniformly mixed carbon sulphur that obtains mixes
Slurries are closed, then carbon sulphur mixed serum is added in the barrel of sand mill and carries out nano ball grinding, rotational speed of ball-mill 1500rpm, ball
Time consuming is 20min；
(2) the carbon sulphur mixed serum after step (1) is dried 10 hours at 90 DEG C in air dry oven, carries out powder
It is broken, it is then transferred into vacuum drying oven, heat fusing 15 hours at 180 DEG C obtain Ketjen black-graphene/sulfur composite positive electrode material
Material；
(3) by the Ketjen black after step (2)-graphene/sulfur composite positive electrode material, acetylene black, sodium alginate according to quality
Than being added to the water for 7.5:1.5:1, lithium-sulphur cell positive electrode slurry presoma is made after mixing, then by anode sizing agent forerunner
Body, which is added in the barrel of sand mill, carries out nano ball grinding, rotational speed of ball-mill 1500rpm, and the time is 40 minutes, and obtaining solid content is
22% lithium-sulphur cell positive electrode slurry；
(4) the lithium-sulphur cell positive electrode slurry after step (3) being coated uniformly on aluminium foil, blade thickness is set as 500um,
It is dried in air dry oven immediately after, drying temperature is 100 DEG C, and the time is 2 hours, and high-sulfur load is obtained after drying
Lithium-sulphur cell positive electrode.
In the present embodiment, the load capacity of sulphur is 9.9mg/cm in the lithium-sulphur cell positive electrode that is prepared2.It will be in the present embodiment
The high-sulfur load lithium-sulphur cell positive electrode and cathode, electrolyte being prepared are assembled into lithium-sulfur cell, and wherein cathode is metal lithium sheet,
Electrolyte is the mixed solution of bis trifluoromethyl sulfonic acid Asia amide lithium, lithium nitrate, 1,3- dioxolanes and glycol dimethyl ether.It will
The lithium-sulfur cell that is prepared carries out cycle performance test, activates for the first time under 0.1C, and specific discharge capacity reaches 970mAh/g, under 1C
First discharge specific capacity is 780mAh/g, and the specific discharge capacity of battery is 530mAh/g after recycling 100 times under 1C, and coulombic efficiency is big
In 97%.
Claims (10)
1. a kind of preparation method of high-sulfur load lithium-sulphur cell positive electrode, which comprises the following steps:
(1) carbon material and sulphur are added to the water, are uniformly mixed and obtain carbon sulphur mixed serum；
(2) the carbon sulphur mixed serum after step (1) is added in sand mill and carries out nano ball grinding, then be dried and crush, so
Heating melting afterwards obtains carbon sulphur composite positive pole；
(3) the carbon sulphur composite positive pole after conductive agent, adhesive and step (2) is added to the water, lithium is made after mixing
Then anode sizing agent presoma is added in sand mill and carries out nano ball grinding by sulphur cell positive electrode slurry presoma, obtain lithium sulphur electricity
Pond anode sizing agent；
(4) the lithium-sulphur cell positive electrode slurry after step (3) is coated uniformly on aluminium foil, obtains high-sulfur load lithium sulphur after drying
Anode.
2. preparation method according to claim 1, which is characterized in that in the step (2) and step (3), nano ball grinding
Revolving speed be 1000-1500rpm, time 20-60min.
3. preparation method according to claim 1, which is characterized in that carbon material is Ketjen black in the step (1), carbon is received
One or more of mitron, Cabot conductive carbon black BP2000, acetylene black, graphene；The mass ratio of the carbon material and sulphur
For 1:(2-9)；The solid content of the carbon sulphur mixed serum is 10%-30%.
4. preparation method according to claim 1, which is characterized in that in the step (3) conductive agent be carbon nanotube,
One or more of Super-P, acetylene black；Described adhesive is aqueous binder, specially sodium carboxymethylcellulose and fourth
One or more of the mixture of benzene rubber, acrylonitrile multiple copolymer, polytetrafluoroethylene (PTFE), sodium alginate.
5. preparation method according to claim 1, which is characterized in that dried in air dry oven in the step (2)
It carries out, controlled at 45-80 DEG C, time 10-24h；Described be melted in vacuum drying oven carries out, controlled at 155-
200 DEG C, time 10-24h.
6. preparation method according to claim 1, which is characterized in that carbon sulphur composite positive pole in the step (3) is led
The mass ratio of electric agent and adhesive is (6-8): (3-1): 1；The solid content of the lithium-sulphur cell positive electrode slurry is 10%-30%.
7. preparation method according to claim 1, which is characterized in that in the step (4), the height of scraper is when coating
200-500um；The drying carries out in air dry oven, and control drying temperature is 60-100 DEG C, drying time 1-6h.
8. a kind of high-sulfur load lithium-sulphur cell positive electrode being prepared such as preparation method of any of claims 1-7,
It is characterized in that, sulphur load capacity is 3-10mg/cm in the lithium-sulphur cell positive electrode2。
9. a kind of lithium-sulfur cell, which is characterized in that including high-sulfur according to any one of claims 8 load lithium-sulphur cell positive electrode, cathode with
And electrolyte.
10. lithium-sulfur cell according to claim 9, which is characterized in that the electrolyte is bis trifluoromethyl sulfonic acid Asia acyl
Amine lithium, lithium nitrate, 1,3-dioxolane and glycol dimethyl ether mixed solution, the cathode be metal lithium sheet.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811390629.6A CN109346678A (en) | 2018-11-21 | 2018-11-21 | A kind of high-sulfur load lithium-sulphur cell positive electrode and preparation method thereof, lithium-sulfur cell |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811390629.6A CN109346678A (en) | 2018-11-21 | 2018-11-21 | A kind of high-sulfur load lithium-sulphur cell positive electrode and preparation method thereof, lithium-sulfur cell |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109346678A true CN109346678A (en) | 2019-02-15 |
Family
ID=65317015
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811390629.6A Pending CN109346678A (en) | 2018-11-21 | 2018-11-21 | A kind of high-sulfur load lithium-sulphur cell positive electrode and preparation method thereof, lithium-sulfur cell |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109346678A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110649222A (en) * | 2019-09-29 | 2020-01-03 | 江西省科学院应用物理研究所 | Preparation method of lithium-sulfur battery positive electrode |
| CN110729453A (en) * | 2019-11-21 | 2020-01-24 | 常州大学 | Lithium-sulfur battery positive pole piece with self-repairing function and preparation method thereof |
| CN111446418A (en) * | 2020-04-17 | 2020-07-24 | 中国航发北京航空材料研究院 | High-sulfur-loading-capacity lithium-sulfur battery positive plate and preparation method thereof |
| CN113228349A (en) * | 2019-05-14 | 2021-08-06 | 株式会社Lg化学 | Sulfur-carbon composite, and positive electrode and lithium secondary battery each containing the sulfur-carbon composite |
| CN114023919A (en) * | 2021-10-20 | 2022-02-08 | 中国科学院上海硅酸盐研究所 | High-capacity sulfur positive electrode and lithium-sulfur battery containing same |
| US11967702B2 (en) | 2019-05-14 | 2024-04-23 | Lg Energy Solution, Ltd. | Sulfur-carbon composite, and cathode and lithium secondary battery each comprising same |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102569816A (en) * | 2012-02-14 | 2012-07-11 | 中南大学 | Positive electrode of lithium sulfur battery and preparation method thereof |
| CN105449170A (en) * | 2014-08-13 | 2016-03-30 | 清华大学 | Method for preparing high-sulfur-content positive electrode material used for lithium-sulfur secondary battery |
| CN105826523A (en) * | 2016-03-17 | 2016-08-03 | 北京理工大学 | Lithium-sulfur battery positive pole material and preparation method thereof |
| CN105932230A (en) * | 2016-04-27 | 2016-09-07 | 长沙矿冶研究院有限责任公司 | Nano-rod porous carbon-sulfur composite cathode material, preparation method thereof and lithium-sulfur battery |
| CN106898746A (en) * | 2017-03-14 | 2017-06-27 | 天津大学 | Hierarchical porous structure nano-sized carbon/sulphur composite and the application in lithium-sulfur cell are prepared by raw material of Hawaii shell |
-
2018
- 2018-11-21 CN CN201811390629.6A patent/CN109346678A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102569816A (en) * | 2012-02-14 | 2012-07-11 | 中南大学 | Positive electrode of lithium sulfur battery and preparation method thereof |
| CN105449170A (en) * | 2014-08-13 | 2016-03-30 | 清华大学 | Method for preparing high-sulfur-content positive electrode material used for lithium-sulfur secondary battery |
| CN105826523A (en) * | 2016-03-17 | 2016-08-03 | 北京理工大学 | Lithium-sulfur battery positive pole material and preparation method thereof |
| CN105932230A (en) * | 2016-04-27 | 2016-09-07 | 长沙矿冶研究院有限责任公司 | Nano-rod porous carbon-sulfur composite cathode material, preparation method thereof and lithium-sulfur battery |
| CN106898746A (en) * | 2017-03-14 | 2017-06-27 | 天津大学 | Hierarchical porous structure nano-sized carbon/sulphur composite and the application in lithium-sulfur cell are prepared by raw material of Hawaii shell |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113228349A (en) * | 2019-05-14 | 2021-08-06 | 株式会社Lg化学 | Sulfur-carbon composite, and positive electrode and lithium secondary battery each containing the sulfur-carbon composite |
| EP3905392A4 (en) * | 2019-05-14 | 2022-02-23 | LG Chem, Ltd. | Sulfur-carbon composite, and cathode and lithium secondary battery each comprising same |
| US11967702B2 (en) | 2019-05-14 | 2024-04-23 | Lg Energy Solution, Ltd. | Sulfur-carbon composite, and cathode and lithium secondary battery each comprising same |
| CN110649222A (en) * | 2019-09-29 | 2020-01-03 | 江西省科学院应用物理研究所 | Preparation method of lithium-sulfur battery positive electrode |
| CN110649222B (en) * | 2019-09-29 | 2023-02-03 | 江西省科学院应用物理研究所 | Preparation method of lithium-sulfur battery positive electrode |
| CN110729453A (en) * | 2019-11-21 | 2020-01-24 | 常州大学 | Lithium-sulfur battery positive pole piece with self-repairing function and preparation method thereof |
| CN110729453B (en) * | 2019-11-21 | 2022-04-26 | 常州大学 | Lithium-sulfur battery positive pole piece with self-repairing function and preparation method thereof |
| CN111446418A (en) * | 2020-04-17 | 2020-07-24 | 中国航发北京航空材料研究院 | High-sulfur-loading-capacity lithium-sulfur battery positive plate and preparation method thereof |
| CN111446418B (en) * | 2020-04-17 | 2021-08-03 | 中国航发北京航空材料研究院 | High-sulfur-loading-capacity lithium-sulfur battery positive plate and preparation method thereof |
| CN114023919A (en) * | 2021-10-20 | 2022-02-08 | 中国科学院上海硅酸盐研究所 | High-capacity sulfur positive electrode and lithium-sulfur battery containing same |
| CN114023919B (en) * | 2021-10-20 | 2023-08-08 | 中国科学院上海硅酸盐研究所 | High-load sulfur positive electrode and lithium sulfur battery containing high-load sulfur positive electrode |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR102239750B1 (en) | Microcapsule type silicon-carbon composite negative electrode material, and manufacturing method and use thereof | |
| CN109346678A (en) | A kind of high-sulfur load lithium-sulphur cell positive electrode and preparation method thereof, lithium-sulfur cell | |
| CN103199258B (en) | Anode material for lithium-ion batteries, anode preparation method and lithium ion battery | |
| CN106784671B (en) | A kind of preparation method of anode material for lithium-ion batteries | |
| CN107689452A (en) | A kind of graphene composite conductive slurry, its preparation method and application | |
| CN102088086B (en) | Method for preparing high-voltage lithium ion battery anode | |
| CN103107319B (en) | Lithium ion battery carbon microsphere negative electrode material and preparation method thereof | |
| CN104617269A (en) | Silicon alloy composite anode material, preparation method and lithium ion battery | |
| CN113690427A (en) | Preparation method of lithium-silicon alloy pole piece, lithium-silicon alloy pole piece and lithium battery | |
| CN106340649A (en) | Preparation method of lithium ferric phosphate cathode slurry | |
| CN105355849A (en) | Lithium battery cathode additive, lithium ion battery, preparation method and uses thereof | |
| CN107086128B (en) | A kind of mixed type electrochmical power source device electrode and preparation method thereof | |
| CN112652770A (en) | Silicon-carbon negative electrode material with low specific surface area and preparation method thereof | |
| CN101567469A (en) | Power polymer lithium ion battery and fabricating process thereof | |
| CN111933892B (en) | Negative plate, preparation method thereof and lithium ion secondary battery comprising negative plate | |
| CN102969509A (en) | Preparation method of lithium ion battery silicon carbon composite material | |
| CN113675365A (en) | Negative plate and lithium ion battery | |
| CN104752682A (en) | Preparation method of sulphur/carbon composite cathode material for lithium sulphur battery | |
| CN107293697B (en) | A kind of power-type lithium ion battery negative electrode material production method | |
| CN106654266A (en) | Preparation method of nano-particle/carbon composite material and electrode battery | |
| CN111613791B (en) | Negative electrode active material, silicon-carbon negative electrode piece and high-energy-density quick-charging lithium ion battery | |
| CN111313023B (en) | High-solid-content semi-solid electrode, preparation method thereof and lithium slurry flow battery comprising electrode | |
| CN113054157A (en) | Double-composite modified spinel lithium manganate positive plate, preparation method thereof and lithium ion battery | |
| CN103515597B (en) | The Preparation method and use of negative material | |
| CN103311521A (en) | Surface-modified graphite negative electrode material, and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190215 |
|
| RJ01 | Rejection of invention patent application after publication |