CN103872299B - A kind of lithium-sulphur cell positive electrode element doping oxide-sulfur composite and preparation method thereof - Google Patents
A kind of lithium-sulphur cell positive electrode element doping oxide-sulfur composite and preparation method thereof Download PDFInfo
- Publication number
- CN103872299B CN103872299B CN201410102869.7A CN201410102869A CN103872299B CN 103872299 B CN103872299 B CN 103872299B CN 201410102869 A CN201410102869 A CN 201410102869A CN 103872299 B CN103872299 B CN 103872299B
- Authority
- CN
- China
- Prior art keywords
- element doping
- lithium
- doping oxide
- sulfur
- positive electrode
- 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.)
- Active
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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
-
- 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
- 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
- H01M4/624—Electric conductive fillers
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- 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
-
- 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 invention discloses a kind of lithium-sulphur cell positive electrode element doping oxide sulfur composite and preparation method thereof.Carried out dispensing, ball mill mixing by element doping oxide and elemental sulfur according to mass ratio, then calcine under 120 DEG C～450 DEG C of inert atmospheres, be incubated 1～48 hour, i.e. prepare lithium-sulfur cell element doping oxide sulfur composite positive pole.Compared with conventional porous carbon/sulfur composite, the composite anode material for lithium sulfur battery utilizing the formula of the present invention and preparation method to prepare shows more preferably corrosion resistance and relatively low electrochemical active surface loss, it is effectively increased the utilization rate of active substance sulfur, and then improves specific capacity and the cycle life of battery.This preparation method is easily operated, with low cost, is suitable to large-scale production, is a kind of to have high-energy-density, environmental friendliness and the lithium-sulphur cell positive electrode composite of the series of advantages such as cheap concurrently.
Description
Technical field
The present invention relates to a kind of lithium-sulphur cell positive electrode element doping oxide-sulfur composite and preparation method thereof, belong to
In inorganic nano material and field of chemical power source.
Background technology
In recent years, along with portable electric appts, electronic equipment for consumption, electric automobile and large-scale power grid are to chemical energy storage
The steady growth of battery requirements, secondary cell has welcome best development opportunity.But, the energy of existing lithium ion battery is close
Degree and cycle life are still insufficient for above-mentioned many application, in the urgent need to having the electrode material of more high power capacity.For many years, use
Negative material (such as silicon and stannum) in the novel high-performance of rechargeable battery has been achieved for remarkable break-throughs, but main restriction because of
Element remains the capacity that positive electrode is relatively low.
Sulfur is the most promising positive electrode of one, and specific capacity is up to 1675mAh/g, is existing based on transition metal
Oxide and about 3-5 times of phosphoric acid salt positive electrode.But, the commercialization of lithium-sulfur cell system based on sulfur electrode is also deposited
In several key issues: (1) elemental sulfur is non-conductive；(2) dissolving of intermediate product polysulfide；(3) electrolyte and polysulfide
The corrosion of carrier carbon material and then the electrode structure that causes are destroyed.The existence of these problems causes the specific capacity of lithium-sulfur cell to decline
Subtracting fast, coulombic efficiency is low and cycle life is short.For many years, substantial amounts of work is devoted to solve the first two problem, is led by use
Electric material, including porous carbon, Graphene and conducting polymer, it is intended to improves their electron conduction and limits polysulfide
Dissolve.But, it is that to cause lithium-sulfur cell cycle life can not reach industrialized requirement important to the attention deficiency of the 3rd problem
One of factor.
Summary of the invention
It is an object of the invention to provide one and there is good corrosion and relatively low electrochemical active surface loss
Element doping oxide-sulfur composite and preparation method thereof, this composite can be used for lithium sulfur battery anode material.
Element doping oxide-sulfur composite of the present invention, including the raw material of following mass ratio:
Element doping oxide 1；
Elemental sulfur 1～10；
Oxide in described element doping oxide is tin ash or titanium dioxide；
Element in described element doping oxide is boron, nitrogen, fluorine, aluminum, manganese, ferrum, cobalt, nickel, copper, zinc, molybdenum, antimony or cerium.
Further, described tin ash doped chemical include boron, nitrogen, fluorine, aluminum, antimony, ferrum, cobalt, nickel, copper, zinc, molybdenum and
Cerium.
Further, described titania additive element includes boron, nitrogen, fluorine, aluminum, manganese, ferrum and copper.
Further, described element doping oxide is single element doping oxide, or multielement codope oxide.
Further, in described element doping oxide, the content of doped chemical is between 0.01wt%-20wt%.
Further, described element doping oxide should have certain specific surface area, and specific surface area is between 50m2/g
To 3000m2Between/g.
Further, the pore volume of described element doping oxide is between 0.2cm3/ g and 4.2cm3Between/g, wherein micropore hole
Hold between 0.05cm3/ g and 2.0cm3Between/g.
Correspondingly, the present invention and then give the preparation of lithium-sulphur cell positive electrode element doping oxide-sulfur composite
Method, comprises the steps:
The first step: the ratio of element doping oxide with elemental sulfur 1:1 in mass ratio～10 is mixed in grinding in ball grinder
Close uniformly；
Second step: by mixture under nitrogen atmosphere or argon inert atmosphere, is that 1～20 DEG C/min heats up with heating rate
To 120～450 DEG C, constant temperature 1～after 48 hours, naturally cool to room temperature, element doping oxide-sulfur composite.
Correspondingly, the present invention furthermore present a kind of lithium sulfur utilizing element doping oxide-sulfur composite to prepare
Battery anode slurry, including the raw material of following mass ratio:
Element doping oxide-sulfur composite 60～90；
Conductive agent 5～30；
Binding agent 5～30；
Described conductive agent is carbon black, graphite, Graphene or activated carbon；
Described binding agent is polyethylene glycol oxide, polyvinylidene fluoride, politef, gelatin or functionalization beta-schardinger dextrin-.
Yet further, the present invention gives the method that lithium-sulphur cell positive electrode prepared by lithium-sulphur cell positive electrode slurry, including
Following step:
1) it is 60～90:5～30:5 in mass ratio by element doping oxide-sulfur composite, conductive agent and binding agent
～the ratio of 30 is fully ground form slurry, then by the slurry coating after mixing on aluminium foil；
2) aluminium foil being coated with slurry is dried 2～12 hours at 40～130 DEG C in vacuum drying oven, obtains lithium sulfur
Anode.
Element doping oxide used in the present invention can derive from market, can be prepared by open preparation method, it is possible to pass through
To the stanniferous or compound of titaniferous and other elements or other elements such as tin ash, titanium dioxide, two hydration stannum dichloride
Compound is prepared by chemical reaction.
Elementary sulfur is dispersed in the basal body structure of element doping oxide as active substance, is in high degree of dispersion state.
Compared with prior art, beneficial effects of the present invention is embodied in:
(1) conventional tin ash is a kind of wide band gap semiconducter, and the tin ash using element-specific to adulterate becomes and leads
Body, after showing more preferable electric conductivity, and elemental sulfur mixing, can be effectively improved the electric conductivity of positive electrode, and then improve single
The reactivity of matter sulfur and and the high rate performance of battery.
(2) compared with conventional carbon carrier, element doping tin ash and titanium dioxide show the most anticorrosive
Property and relatively low electrochemical active surface loss, the utilization rate of elemental sulfur can be greatly improved.
(3) in element doping oxide, the existence of multi-stage porous can effectively disperse elemental sulfur, simultaneously element doping oxide-sulfur
Gap structure unnecessary in composite is conducive to the infiltration of electrolyte and the transmission of lithium ion, can be effectively improved electrode material
Ionic conductivity.
Method prepared by composite of the present invention is heat treating process, and course of reaction is simple to operate, controls easily, raw material simultaneously
Cheap it is easy to get, is conducive to high-volume industrialization to produce.Meanwhile, the excellent performance of the composite that the method is prepared, it is expected to
Electrokinetic cell and energy storage field obtain huge development.
Accompanying drawing explanation
Fig. 1 is that the composite of embodiment 1 is at 0.1C (1C=1675mAg-1) specific discharge capacity figure under multiplying power；
Fig. 2 is that the composite of embodiment 2 is at 0.1C (1C=1675mAg-1) specific discharge capacity figure under multiplying power；
Fig. 3 is that the composite of embodiment 3 is at 0.1C (1C=1675mAg-1) specific discharge capacity figure under multiplying power；
Fig. 4 is that the composite of embodiment 4 is at 0.1C (1C=1675mAg-1) specific discharge capacity figure under multiplying power；
Fig. 5 is that the composite of embodiment 5 is at 0.1C (1C=1675mAg-1) specific discharge capacity figure under multiplying power；
Fig. 6 is that the composite of embodiment 6 is at 0.1C (1C=1675mAg-1) specific discharge capacity figure under multiplying power.
Detailed description of the invention
The present invention is described in detail, in the illustrative examples of this present invention below in conjunction with accompanying drawing and specific embodiment
And explanation is used for explaining the present invention, but not as a limitation of the invention.
Embodiment 1
Preparation method and the compliance test result of lithium-sulphur cell positive electrode element doping oxide-sulfur composite are as follows:
The first step: by uniform in grinding in ball grinder to N doping tin ash and elemental sulfur 1:1.5 in mass ratio；
Second step: in nitrogen gas atmosphere, is 1 DEG C/min bar by N doping tin ash sulfur mixture at heating rate
Being heated to 150 DEG C under part, constant temperature is cooled to room temperature after 10 hours can obtain composite；
3rd step: by the ratio of composite, conductive agent graphite and binding agent politef 70:20:10 in mass ratio
It is fully ground form slurry, then the slurry coating after mixing is made pole piece on aluminium foil；
4th step: pole piece is cut to the disk of a diameter of 1.6cm after being dried 12 hours in vacuum drying oven at 60 DEG C
Standby.
With cut size pole piece as positive pole, do negative pole with lithium sheet, select polypropylene to make barrier film, choose 1mol/L bis-(three
Methyl fluoride sulphonyl) imine lithium is electrolyte, 0.1mol/L lithium nitrate does additive, solvent volume ratio 1,3-dioxolane: diformazan
Ether=1:1, is assembled into CR2032 type button cell.Discharge and recharge blanking voltage is respectively 1.7V and 3.1V, at 0.1C(1C=
1675mA/g) under multiplying power, the first discharge specific capacity of battery reaches 1281mAh/g, after 50 times circulate, and the specific capacity of battery
More than 1150mAh/g can also be maintained at.The most as shown in Figure 1.
Embodiment 2
Preparation method and the compliance test result of lithium-sulphur cell positive electrode element doping oxide-sulfur composite are as follows:
The first step: by uniform in grinding in ball grinder to nitrogen-doped titanium dioxide and elemental sulfur 1:1.5 in mass ratio；
Second step: in argon gas atmosphere, is 3 DEG C/min bar by nitrogen-doped titanium dioxide sulfur mixture at heating rate
Being heated to 150 DEG C under part, constant temperature is cooled to room temperature after 10 hours can obtain composite；
3rd step: by the ratio of composite, conductive agent carbon black and binding agent polyethylene glycol oxide 60:20:20 in mass ratio
It is fully ground form slurry, then the slurry coating after mixing is made pole piece on aluminium foil；
4th step: pole piece is cut to the disk of a diameter of 1.6cm after being dried 10 hours in vacuum drying oven at 110 DEG C
Standby.
Remaining step is same as in Example 1, tests same as in Example 1.The first discharge specific capacity of battery reaches
1472mAh/g, after 200 times circulate, the specific capacity of battery can also be maintained at more than 1200mAh/g.The most as shown in Figure 2.
Embodiment 3
Preparation method and the compliance test result of lithium-sulphur cell positive electrode element doping oxide-sulfur composite are as follows:
The first step: by uniform in grinding in ball grinder to prepared Fluorin doped tin ash and elemental sulfur 1:1 in mass ratio；
Second step: in nitrogen gas atmosphere, is 5 DEG C/min bar by Fluorin doped tin ash sulfur mixture at heating rate
Being heated to 155 DEG C under part, constant temperature is cooled to room temperature after 24 hours can obtain composite；
3rd step: composite, conductive agent Graphene are fully ground with the ratio of binding agent gelatin 90:5:5 in mass ratio
Wear into slurry, then the slurry coating after mixing is made pole piece on aluminium foil；
4th step: pole piece is cut to the disk of a diameter of 1.6cm after being dried 12 hours in vacuum drying oven at 40 DEG C
Standby.
Remaining step is same as in Example 1, tests same as in Example 1.The first discharge specific capacity of battery reaches
1430mAh/g, after 50 times circulate, the specific capacity of battery can also be maintained at more than 1200mAh/g.The most as shown in Figure 3.
Embodiment 4
Preparation method and the compliance test result of lithium-sulphur cell positive electrode element doping oxide-sulfur composite are as follows:
The first step: by uniform in grinding in ball grinder to prepared aluminum doped titanium dioxide and elemental sulfur 1:2 in mass ratio；
Second step: in nitrogen gas atmosphere, is 10 DEG C/min by aluminum doped titanium dioxide sulfur mixture at heating rate
Under the conditions of be heated to 180 DEG C, constant temperature is cooled to room temperature after 18 hours can obtain composite；
3rd step: by composite, conductive agent Graphene with binding agent polyvinylidene fluoride 80:10:10's in mass ratio
Ratio is fully ground form slurry, then the slurry coating after mixing is made on aluminium foil pole piece；
4th step: pole piece is cut to the disk of a diameter of 1.6cm after being dried 10 hours in vacuum drying oven at 90 DEG C
Standby.
Remaining step is same as in Example 1, tests same as in Example 1.The first discharge specific capacity of battery reaches
1529mAh/g, after 200 times circulate, the specific capacity of battery can also be maintained at more than 1100mAh/g.The most as shown in Figure 4.
Embodiment 5
Preparation method and the compliance test result of lithium-sulphur cell positive electrode element doping oxide-sulfur composite are as follows:
The first step: by prepared copper, zinc and ferrum codope tin ash and elemental sulfur 1:10 in mass ratio in ball mill
Grind uniformly；
Second step: in argon gas atmosphere, is 20 by copper, zinc and manganese codoped tin ash mixture at heating rate
DEG C/min under the conditions of be heated to 450 DEG C, constant temperature is cooled to room temperature after 1 hour can obtain composite；
3rd step: by the ratio of composite, conductive agent graphite and binding agent politef 70:15:15 in mass ratio
It is fully ground form slurry, then the slurry coating after mixing is made pole piece on aluminium foil；
4th step: pole piece is cut to the disk of a diameter of 1.6cm after being dried 2 hours in vacuum drying oven at 130 DEG C
Standby.
Remaining step is same as in Example 1, tests same as in Example 1.The first discharge specific capacity of battery reaches
1310mAh/g, after 50 times circulate, the specific capacity of battery can also be maintained at about 1000mAh/g.The most as shown in Figure 5.
Embodiment 6
Preparation method and the compliance test result of lithium-sulphur cell positive electrode element doping oxide-sulfur composite are as follows:
The first step: by prepared copper, ferrum, manganese codoped titanium dioxide and elemental sulfur 1:1.5 in mass ratio in ball mill
Grind uniformly；
Second step: in nitrogen gas atmosphere, is 1 DEG C/min bar by N doping tin ash sulfur mixture at heating rate
Being heated to 150 DEG C under part, constant temperature is cooled to room temperature after 10 hours can obtain composite；
3rd step: composite, conductive agent carbon black are fully ground with the ratio of binding agent gelatin 60:30:10 in mass ratio
Wear into slurry, then the slurry coating after mixing is made pole piece on aluminium foil；
4th step: pole piece is cut to the disk of a diameter of 1.6cm after being dried 8 hours in vacuum drying oven at 100 DEG C
Standby.
Remaining step is same as in Example 1, tests same as in Example 1.The first discharge specific capacity of battery reaches
1385mAh/g, after 100 times circulate, the specific capacity of battery can also be maintained at about 750mAh/g.The most as shown in Figure 6.
Embodiment 7
Preparation method and the compliance test result of lithium-sulphur cell positive electrode element doping oxide-sulfur composite are as follows:
The first step: by equal in grinding in ball grinder to prepared cobalt, nickel doping stannic oxide and elemental sulfur 1:2 in mass ratio
Even；
Second step: in nitrogen gas atmosphere, is 1 DEG C/min bar by N doping tin ash sulfur mixture at heating rate
Being heated to 150 DEG C under part, constant temperature is cooled to room temperature after 10 hours can obtain composite；
3rd step: by composite, conductive agent activated carbon with binding agent polyvinylidene fluoride 60:10:30's in mass ratio
Ratio is fully ground form slurry, then the slurry coating after mixing is made on aluminium foil pole piece；
4th step: pole piece is cut to the disk of a diameter of 1.6cm after being dried 12 hours in vacuum drying oven at 60 DEG C
Standby.
Remaining step is same as in Example 1, tests same as in Example 1.The first discharge specific capacity of battery reaches
1217mAh/g, after 50 times circulate, the specific capacity of battery can also be maintained at about 1000mAh/g.
Embodiment 8
Preparation method and the compliance test result of lithium-sulphur cell positive electrode element doping oxide-sulfur composite are as follows:
The first step: by uniform in grinding in ball grinder to prepared boron doped titanic oxide and elemental sulfur 1:2 in mass ratio；
Second step: in nitrogen gas atmosphere, is 1 DEG C/min bar by N doping tin ash sulfur mixture at heating rate
Being heated to 150 DEG C under part, constant temperature is cooled to room temperature after 10 hours can obtain composite；
3rd step: by composite, conductive agent carbon black with binding agent functionalization beta-schardinger dextrin-70:20:10's in mass ratio
Ratio is fully ground form slurry, then the slurry coating after mixing is made on aluminium foil pole piece；
4th step: pole piece is cut to the disk of a diameter of 1.6cm after being dried 12 hours in vacuum drying oven at 90 DEG C
Standby.
Remaining step is same as in Example 1, tests same as in Example 1.The first discharge specific capacity of battery reaches
1545mAh/g, after 50 times circulate, the specific capacity of battery can also be maintained at more than 1200mAh/g.
Embodiment 9
Preparation method and the compliance test result of lithium-sulphur cell positive electrode element doping oxide-sulfur composite are as follows:
The first step: by uniform in grinding in ball grinder to prepared molybdenum doping tin ash and elemental sulfur 1:10 in mass ratio；
Second step: in nitrogen gas atmosphere, is 3 DEG C/min bar by molybdenum doping tin ash sulfur mixture at heating rate
155 DEG C it are heated under part, 2 hours post-heating of constant temperature to 300 DEG C of constant temperature 1 hour, it is cooled to room temperature and can obtain composite；
3rd step: by the ratio of composite, conductive agent carbon black and binding agent politef 70:20:10 in mass ratio
It is fully ground form slurry, then the slurry coating after mixing is made pole piece on aluminium foil；
4th step: pole piece is cut to the disk of a diameter of 1.6cm after being dried 12 hours in vacuum drying oven at 110 DEG C
Standby.
Remaining step is same as in Example 1, tests same as in Example 1.The first discharge specific capacity of battery reaches
1465mAh/g, after 50 times circulate, the specific capacity of battery can also be maintained at more than 1300mAh/g.
Embodiment 10
Preparation method and the compliance test result of lithium-sulphur cell positive electrode element doping oxide-sulfur composite are as follows:
The first step: by uniform in grinding in ball grinder to prepared Fluorin doped titanium dioxide and elemental sulfur 1:10 in mass ratio；
Second step: remaining step is the same as in Example 9, tests same as in Example 1.The first discharge specific capacity of battery reaches
To 1532mAh/g, after 200 times circulate, the specific capacity of battery can also be maintained at more than 1250mAh/g.
Embodiment 11
Preparation method and the compliance test result of lithium-sulphur cell positive electrode element doping oxide-sulfur composite are as follows:
The first step: by uniform in grinding in ball grinder to prepared stibium doping stannic oxide and elemental sulfur 1:10 in mass ratio；
Second step: in argon gas atmosphere, is 5 DEG C/min by element doping tin ash sulfur mixture at heating rate
Under the conditions of be heated to 300 DEG C, constant temperature is cooled to room temperature after 2 hours can obtain composite；
3rd step: remaining step is same as in Example 1, tests same as in Example 1.The first discharge specific capacity of battery reaches
To 1428mAh/g, after 50 times circulate, the specific capacity of battery can also be maintained at more than 1200mAh/g.
Embodiment 12
Preparation method and the compliance test result of lithium-sulphur cell positive electrode element doping oxide-sulfur composite are as follows:
The first step: by equal in grinding in ball grinder to prepared aluminum, Fe2O3 doping titanium dioxide and elemental sulfur 1:10 in mass ratio
Even；
Second step: remaining step is identical with embodiment 11, tests same as in Example 1.The first discharge specific capacity of battery
Reaching 1412mAh/g, after 50 times circulate, the specific capacity of battery can also be maintained at more than 1150mAh/g.
In above-mentioned element doping oxide, the content of doped chemical is between 0.01wt%-20wt%.
Above-mentioned element doping oxide specific surface area is between 50m2/ g to 3000m2Between/g.
The pore volume of above-mentioned element doping oxide is between 0.2cm3/ g and 4.2cm3Between/g, wherein Micropore volume between
0.05cm3/ g and 2.0cm3Between/g.
Above content is to combine concrete preferred implementation further description made for the present invention, it is impossible to assert
The detailed description of the invention of the present invention is only limitted to this, for general technical staff of the technical field of the invention, is not taking off
On the premise of present inventive concept, it is also possible to make some simple deduction or replace, all should be considered as belonging to the present invention by institute
The claims submitted to determine scope of patent protection.
Claims (7)
1. lithium-sulphur cell positive electrode element doping oxide-sulfur composite, it is characterised in that include following mass ratio
Raw material:
Element doping oxide 1；
Elemental sulfur 10～1；
Oxide in described element doping oxide is tin ash or titanium dioxide；
Described element doping oxide is single element doping oxide, or multielement codope oxide；
When described element doping oxide is tin ash, doped chemical include boron, nitrogen, fluorine, aluminum, ferrum, cobalt, nickel, copper, zinc,
Molybdenum and cerium；
When described element doping oxide is titanium dioxide, doped chemical includes boron, nitrogen, fluorine, aluminum, manganese, ferrum and copper.
A kind of lithium-sulphur cell positive electrode element doping oxide-sulfur composite the most according to claim 1, its feature exists
In, in described element doping oxide, the content of doped chemical is between 0.01wt%-20wt%.
A kind of lithium-sulphur cell positive electrode element doping oxide-sulfur composite the most according to claim 1, its feature exists
In, described element doping oxide has certain specific surface area, and specific surface area is between 50m2/ g to 3000m2Between/g.
A kind of lithium-sulphur cell positive electrode element doping oxide-sulfur composite the most according to claim 1, its feature exists
In, the pore volume of described element doping oxide is between 0.2cm3/ g and 4.2cm3Between/g, wherein Micropore volume is between 0.05cm3/
G and 2.0cm3Between/g.
5. a preparation side based on the element doping oxide of the lithium-sulphur cell positive electrode described in claim 1-sulfur composite
Method, it is characterised in that comprise the steps:
The first step: the ratio of element doping oxide with elemental sulfur 1:1 in mass ratio～10 is mixed all in grinding in ball grinder
Even；
Second step: by mixture under nitrogen atmosphere or argon inert atmosphere, is that 1～20 DEG C/min is warming up to heating rate
120～450 DEG C, constant temperature 1～after 48 hours, naturally cool to room temperature, element doping oxide-sulfur composite.
6. the lithium prepared based on the lithium-sulphur cell positive electrode element doping oxide-sulfur composite described in claim 1
Sulphur cell positive electrode slurry, it is characterised in that include the raw material of following mass ratio:
Element doping oxide-sulfur composite 60～90；
Conductive agent 5～30；
Binding agent 5～30；
Described conductive agent is carbon black, graphite, Graphene or activated carbon；
Described binding agent is polyethylene glycol oxide, polyvinylidene fluoride, politef, gelatin or functionalization beta-schardinger dextrin-.
7. the method preparing lithium-sulphur cell positive electrode based on the lithium-sulphur cell positive electrode slurry described in claim 6, its feature exists
In, comprise the steps:
1) it is 60～90:5～30:5～30 in mass ratio by element doping oxide-sulfur composite, conductive agent and binding agent
Ratio be fully ground form slurry, then by the slurry coating after mixing on aluminium foil；
2) aluminium foil being coated with slurry is dried 2～12 hours at 40～130 DEG C in vacuum drying oven, obtains lithium-sulfur cell
Positive pole.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410102869.7A CN103872299B (en) | 2014-03-19 | 2014-03-19 | A kind of lithium-sulphur cell positive electrode element doping oxide-sulfur composite and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410102869.7A CN103872299B (en) | 2014-03-19 | 2014-03-19 | A kind of lithium-sulphur cell positive electrode element doping oxide-sulfur composite and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103872299A CN103872299A (en) | 2014-06-18 |
| CN103872299B true CN103872299B (en) | 2017-01-04 |
Family
ID=50910611
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410102869.7A Active CN103872299B (en) | 2014-03-19 | 2014-03-19 | A kind of lithium-sulphur cell positive electrode element doping oxide-sulfur composite and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103872299B (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104201392B (en) * | 2014-08-20 | 2016-06-15 | 中南大学 | The preparation method of a kind of lithium sulphur battery electrode |
| CN107068981A (en) * | 2016-12-29 | 2017-08-18 | 中国电子科技集团公司第十八研究所 | Lithium-sulfur battery positive electrode material containing titanium diboride |
| CN107749473A (en) * | 2017-10-16 | 2018-03-02 | 河源广工大协同创新研究院 | A kind of preparation method of nano-sulfur/nitrogen-doped titanium dioxide composite positive pole |
| KR101965192B1 (en) * | 2017-10-27 | 2019-04-03 | 이화여자대학교 산학협력단 | Metal oxide nanosheet-sulfur nanocomposite and lithium-sulfur battery using the same |
| CN108183214B (en) * | 2017-12-27 | 2020-04-14 | 肇庆市华师大光电产业研究院 | Preparation method of nano sulfur/tungsten nitrogen co-doped titanium dioxide composite positive electrode material |
| EP3505943B1 (en) * | 2017-12-29 | 2020-05-20 | Siemens Aktiengesellschaft | Detection of an electrical overvoltage |
| CN109713313B (en) * | 2018-12-29 | 2020-10-09 | 珠海冠宇电池股份有限公司 | Lithium-sulfur battery positive plate and preparation method thereof and lithium-sulfur battery |
| CN109713282B (en) * | 2018-12-29 | 2020-10-09 | 珠海冠宇电池股份有限公司 | Lithium-sulfur battery positive electrode material, preparation method thereof and lithium-sulfur battery |
| CN113224282B (en) * | 2021-03-26 | 2022-10-04 | 浙江理工大学 | LDH-based oxide coated sulfur particle composite cathode material for lithium-sulfur battery and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102683659A (en) * | 2012-05-31 | 2012-09-19 | 中国科学院物理研究所 | Lithium-sulphur battery anode material and preparation method thereof |
| CN102945966A (en) * | 2012-12-07 | 2013-02-27 | 中国科学院上海硅酸盐研究所 | Positive pole composite system of lithium sulphur battery containing catalytic additive |
| CN103367791A (en) * | 2013-07-15 | 2013-10-23 | 中国科学院化学研究所 | Novel lithium ion battery |
| CN103579590A (en) * | 2013-05-09 | 2014-02-12 | 中国地质大学（武汉） | Preparation method for coating anode material of lithium battery |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100484642B1 (en) * | 2002-09-23 | 2005-04-20 | 삼성에스디아이 주식회사 | Positive active material for lithium-sulfur battery and method for preparing the same |
-
2014
- 2014-03-19 CN CN201410102869.7A patent/CN103872299B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102683659A (en) * | 2012-05-31 | 2012-09-19 | 中国科学院物理研究所 | Lithium-sulphur battery anode material and preparation method thereof |
| CN102945966A (en) * | 2012-12-07 | 2013-02-27 | 中国科学院上海硅酸盐研究所 | Positive pole composite system of lithium sulphur battery containing catalytic additive |
| CN103579590A (en) * | 2013-05-09 | 2014-02-12 | 中国地质大学（武汉） | Preparation method for coating anode material of lithium battery |
| CN103367791A (en) * | 2013-07-15 | 2013-10-23 | 中国科学院化学研究所 | Novel lithium ion battery |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103872299A (en) | 2014-06-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103872299B (en) | A kind of lithium-sulphur cell positive electrode element doping oxide-sulfur composite and preparation method thereof | |
| CN107946576B (en) | High-rate graphite negative electrode material, preparation method thereof and lithium ion battery | |
| CN103078087B (en) | A kind of preparation method of lithium titanate/carbon nano tube composite cathode material | |
| CN105098185A (en) | Composite cathode material, preparation method thereof, lithium ion secondary battery negative plate and lithium ion secondary battery | |
| CN104966812A (en) | Three-dimensional porous quasi-graphene loaded molybdenum disulfide composite and preparation method thereof | |
| WO2019062495A1 (en) | Carbon material and asphalt-based negative electrode material for sodium-ion battery, and preparation method therefor and applications thereof | |
| CN103066265A (en) | Sodium ion battery negative pole active substance and preparation method and application thereof | |
| US20220077456A1 (en) | Core-shell nickel ferrite and preparation method thereof, nickel ferrite@c material and preparation method and application thereof | |
| Huang et al. | Outstanding electrochemical performance of N/S co-doped carbon/Na3V2 (PO4) 3 hybrid as the cathode of a sodium-ion battery | |
| CN104993118A (en) | Synthesizing method for lithium-ion negative electrode material of Li4Ti5O12/C | |
| CN104022269B (en) | A kind of native graphite and MnO composite high-performance electrode material and preparation method thereof | |
| CN106374086B (en) | Nano lithium titanate-graphene composite material and preparation method thereof | |
| CN103441248A (en) | High-specific-capacity and long-life type N-doped carbon microsphere/sulphur composited anode material and preparation method thereof | |
| CN110767901A (en) | Preserved plum-shaped iron diselenide electrode material and preparation method and application thereof | |
| CN107946564B (en) | Rich in Na4Mn2O5/Na0.7MnO2Composite material and preparation method and application thereof | |
| CN102263240A (en) | Lithium ion secondary battery, anode, and manufacturing method and charging and discharging method for anode | |
| CN105702956A (en) | Negative material for sodium-ion battery and preparation method of negative material | |
| WO2016165262A1 (en) | Preparation method for doped lithium titanate negative electrode material | |
| CN107785557B (en) | Preparation method of lithium-rich manganese-based layered material based on lanthanum doping and surface oxygen vacancy modification combined mechanism, product and application thereof | |
| CN113644244B (en) | Chromium oxide/carbon fluoride/highly conductive substance composite material for lithium primary battery | |
| CN105304866B (en) | A kind of lithium-sulphur cell positive electrode containing metal magnesium powder and preparation method thereof | |
| CN105810901A (en) | Ti<3+>/Ti<4+> mixed-valence lithium titanate negative electrode material doped with iron element and preparation of negative electrode material | |
| CN105375029A (en) | Ternary silicate composite cathode material and preparation method therefor | |
| CN101265571A (en) | Lithium ionic cell cathode silicon based compound material preparation method | |
| CN110867607A (en) | Method for reducing preparation cost of solid-state battery of lithium battery by doping modification |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |