CN104659406B - Lithium-sulfur battery and preparation method thereof - Google Patents
Lithium-sulfur battery and preparation method thereof Download PDFInfo
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- CN104659406B CN104659406B CN201510088422.3A CN201510088422A CN104659406B CN 104659406 B CN104659406 B CN 104659406B CN 201510088422 A CN201510088422 A CN 201510088422A CN 104659406 B CN104659406 B CN 104659406B
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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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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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Abstract
The invention belongs to the field of lithium-sulfur batteries and particularly relates to a lithium-sulfur battery and a preparation method thereof. The lithium-sulfur battery comprises a cathode, an anode, an isolation film, an electrolyte and an outer packing, wherein the cathode comprises a current collector and a coating layer, and an active substance in the coating layer at least contains one of elemental sulfur, a sulfur-based compound or a sulfur composite; and furthermore, a polymer reticular structure is further distributed in the coating layer of the cathode, and the anode does not contain the polymer reticular structure. The uniform polymer network structure is distributed in the coating of the cathode of the lithium-sulfur battery provided by the invention, so that lithium sulfides generated in a discharge process are tightly fixed; meanwhile, a selected high polymer has a special structure, namely monomers symmetrically having crosslinking points as many as possible; such monomers have strong ion conductive capability and cannot reduce the electrochemical performance of the lithium-sulfur battery; and the polymer network structure is only distributed on one side of the cathode, and not arranged on one side of the anode, so that the using amount of the polymer can be reduced, and the using cost of raw materials is reduced.
Description
Technical field
The invention belongs to lithium-sulfur cell field, more particularly to a kind of lithium-sulfur cell and preparation method thereof.
Background technology
Since 1991, material with carbon element it is creative apply to field of lithium ion battery, and bring the revolutionary change in the field
Change, i.e., efficiently and safety is carried out after multiple discharge and recharge, it is just widely applied to mobile phone, video camera, notebook electricity
On brain and other portable electronics.Compared with traditional plumbic acid, Ni-Cd, MH-Ni battery, lithium ion battery has higher
Specific volume energy density, weight/power ratio energy density, more preferable environment friendly, less self discharge and longer cycle life
Deng being 21st century preferable movable electrical appliances power supply, electric car power supply and electricity storage station electrical storage device.
However as the raising of life taste, people propose lighter, thinner, less, more longlasting, valency to mobile electrical appliance
The lower new demand of lattice, just to the power supply device of these equipment proposes new requirement accordingly；Energy density is higher, price just
Preferably；Among these power supply device (battery) energy density is closely bound up with Consumer's Experience, enjoys the concern of consumers in general, and shows rank
The method of Duan Tigao battery energy densities is concentrated mainly on the new positive/negative material of exploitation, develops new positive electrode to electricity
It is especially pronounced that pond energy density lifts effect.
The positive electrode of commercialization at present is mainly the lithium transition-metal oxide of stratiform or spinel structure (such as cobalt acid
Lithium, LiMn2O4) and olivine structural LiFePO4 etc..Cobalt acid lithium (LiCoO2) the relatively large (275mAh/ of theoretical capacity
G), but actual discharge capacity only 160mAh/g or so, and its price is high, there is certain toxicity, and the positive electrode is when overcharging
Easily there are exothermal decomposition reactions, be not only decreased obviously battery capacity, while also resulting in threat to cell safety.LiMn2O4
(LiMn2O4) theoretical capacity be 148mAh/g, actual capacity is less than 130mAh/g, and its compacted density is not high, energy density
Low, stability is poor, and lattice deformability is easily caused in charge and discharge process, causes cycle efficieny low.LiFePO4 (LiFePO4)
Theoretical capacity be 172mAh/g, but the positive electrode compacted density is low, and the battery core energy density for preparing is corresponding less.On
Conventional anode material for lithium-ion batteries capacity is stated universal not high, while also there are problems that, it is impossible to meet battery exploitation need
Ask.
The theoretical specific capacity of elemental sulfur is 1675mAh/g, and the theory of the positive electrode for significantly larger than commercially using at present must
Capacity, becomes the major trend of present battery development.But in charge and discharge process, elemental sulfur can be converted into polysulfide, and
Polysulfide can be dissolved in liquid organic solution liquid, cause the loss of the active substance in cyclic process, more seriously, molten
The sulfide of solution will separate out to form dendrite in negative pole, with the risk for greatly piercing through isolating membrane, so as to cause the safety of battery
Property extreme difference.
For the lithium sulfide problems of dissolution that lithium-sulfur cell negative electrode is formed in charge and discharge process, it is necessory to develop one kind
New lithium-sulfur cell system, can solve lithium-sulfur cell lithium sulfide dissolving diffusion problem, and not affect the electrification of lithium-sulfur cell
Learn performance.
The content of the invention
It is an object of the invention to：For the deficiencies in the prior art, and provide a kind of new lithium-sulfur cell system and the lithium
The preparation method of sulfur battery：Be distributed with uniform polymer network structure in the lithium-sulfur cell cathode, tightly will electric discharge
The lithium sulfide generated in overshoot is fixed up, meanwhile, the high molecular polymer of selection has special structure：Symmetrical has
The monomer of many crosslinking points as far as possible；This kind of monomer ion conductive capability is strong, will not reduce the chemical property of lithium-sulfur cell；This gathers
Polymeric network structure is distributed only over negative electrode side, and anode side is not contained, and can reduce the consumption of polymer, reduces raw material
Use cost.
To achieve these goals, the present invention is adopted the following technical scheme that：
A kind of lithium-sulfur cell, is made up of negative electrode, anode, isolating membrane, electrolyte and outer package,
Negative electrode：It is made up of collector and overlay, the cathode active material in overlay at least contains elemental sulfur, sulfation
One kind in compound and sulfur compound；The elemental sulfur includes Sublimed Sulfur and/or high purity sulphur；Sulfur-based compound includes organic sulfide
Thing, Li2SnIn at least one, wherein, n >=1；The sulfur compound includes sulfur/carbon complex, sulfur/conductive polymer composite
With at least one in sulfur/inorganic oxide；
Anode：For lean lithium material and/or rich lithium material；The rich lithium material is lithium metal；The lean lithium material includes carbon
At least one in class material, alloy type material, metal-oxide series, metal nitride and carbon compound；
Isolating membrane：The component of function is turned on electronic isolation, ion；
Electrolyte：It is made up of lithium salts, nonaqueous solvent and additive；
Also it is distributed with derivatized polymers, and anode in cathode-coated layer and does not contain derivatized polymers.
The derivatized polymers being distributed in the cathode-coated layer include the high molecular polymer with symmetrical structure,
Symmetrical or axial symmetry centered on the symmetrical structure, the high molecular symmetrical centre is single atom.
In the cathode-coated layer be distributed derivatized polymers include following structure high polymer monomer polymerization and
Into polymer：
Wherein：
R1 is linear alkyl chain, the alkyl chain containing side base or the segment containing phenyl ring.
R2 is for acrylic or containing the acrylate-based of α-side base.
The high polymer monomer is selected from season nonyl tetra-acrylate, season nonyl tetrol four (Alpha-Methyl) acrylate, season nonyl
Tetrol four (α-ethyl) acrylate, tetramethylol methane tetraacrylate, tetramethylolmethane four (Alpha-Methyl) acrylate, tetramethylolmethane
Four (α-ethyl) acrylate, 1,6- diyl double [oxygen (2- carboxylic propyl group -1,3- diyls)] diacrylate, bisphenol-A dimethyl
At least one monomer in acrylate, bisphenol-A glycerol double methyl methacrylate is polymerized.
Derivatized polymers in the cathode-coated layer are uniformly distributed in cathode-coated layer, the polymer
Quality accounts for the 0.1%-20% of whole cathode-coated layer quality.
Derivatized polymers in the cathode-coated layer are formed or/and polymer transfer infiltration for monomer in situ polymerization
Form.
A kind of preparation method of above-mentioned lithium-sulfur cell, it is characterised in that at least including following step：
Step 1, polymer paste configuration：High molecular component is uniformly mixed with solvent, the slurry of high molecular component is obtained
It is stand-by；
It is prepared by step 2, cathode electrode：Will be a kind of in the complex at least containing sulphur simple substance, the compound of sulfur and sulfur
Active material of cathode, conductive agent, bonding agent and solvent mix homogeneously prepare slurry, apply obtain on a current collector afterwards
Cathode sheet；
Step 3, by slurry obtained in step 1 pole piece that step 2 is obtained is sprayed at, and is permeated through fully, is reacted, goes
Obtain that the cathode sheet of derivatized polymers is distributed with after solvation；
Step 4, the preparation of finished product lithium-sulfur cell：The cathode sheets that step 3 is obtained obtain naked with anode strip, isolating membrane assembling
Battery core, enters afterwards shell/enter bag, baking, fluid injection, standing, chemical conversion, shaping and obtains finished product lithium-sulfur cell.
High molecular component described in step 1 is high polymer monomer or/and high molecular polymer.
High polymer monomer described in step 1 is the high polymer monomer with symmetrical structure, including season nonyl tetra-acrylate,
Season four (Alpha-Methyl) acrylate of nonyl tetrol, season nonyl tetrol four (α-ethyl) acrylate, tetramethylol methane tetraacrylate, season penta
Tetrol four (Alpha-Methyl) acrylate, tetramethylolmethane four (α-ethyl) acrylate, 1,6- diyl it is double [oxygen (2- carboxylics propyl group -1,
3- diyls)] diacrylate, bisphenol a dimethacrylate, at least one in bisphenol-A glycerol double methyl methacrylate；
High molecular polymer described in step 1 is the high molecular polymer with symmetrical structure.
Solvent described in step 1 includes at least one in ethanol, acetone and N-methyl ketopyrrolidine.
The beneficial effects of the present invention is：Uniform polymer network is distributed with the lithium-sulfur cell cathode of the present invention
Structure, the lithium sulfide generated in overshoot being fixed up tightly, meanwhile, it is special that the high molecular polymer of selection has
Structure：The symmetrical monomer with as far as possible many crosslinking points；This kind of monomer ion conductive capability is strong, will not reduce lithium-sulfur cell
Chemical property；The polymer network structure is distributed only over negative electrode side, and anode side is not contained, and can reduce polymer
Consumption, reduce raw material use cost.
Specific embodiment
The present invention and its advantage are described in detail with reference to specific embodiment, but the embodiment party of the present invention
Formula not limited to this.
It is prepared by comparative example 1, cathode sheets：By sulfur-graphene complex (accounting for the 95% of whole cathode-coated layer weight) with it is viscous
Agent and solvent are connect, slurry is obtained after being sufficiently stirred for, afterwards process is coated, colding pressing obtains cathode sheets.
It is prepared by finished product battery core：The cathode sheets for preparing, metal lithium bands and isolating membrane winding is obtained into naked battery core, is used
Aluminum plastic film for packaging bag carry out into bag encapsulate, post-drying, fluid injection, standing, chemical conversion, shaping, degasification after, after finally giving molding
Battery core.
It is prepared by comparative example 2, cathode sheets：By sulfur-graphene complex (accounting for the 95% of whole cathode-coated layer weight) with it is viscous
Agent and solvent are connect, slurry is obtained after being sufficiently stirred for, afterwards process is coated, colding pressing obtains cathode sheets.
It is prepared by anode strip：Graphite, conductive agent, bonding agent and solvent are sufficiently stirred for obtain anode slurry, are applied afterwards
On a current collector, Jing colding pressing, after slitting welding obtain anode strip.
It is prepared by lithium-rich anode strip：On above-mentioned anode strip top layer, layer of metal lithium band is combined, prepares lithium-rich anode strip.
It is prepared by finished product battery core：The cathode sheets for preparing, lithium-rich anode strip and isolating membrane winding is obtained into naked battery core, is made
With aluminum plastic film be packaging bag carry out into bag encapsulate, post-drying, fluid injection, standing, chemical conversion, shaping, degasification after, finally give molding
Battery core afterwards.
Comparative example 3, polymer solution configuration：By ethyl acrylate：Di-isopropyl peroxydicarbonate：Ethanol=20：
0.5：79.5 ratio, stirs first standby by weighing ethyl acrylate, ethanol, adds in using first 1 month afterwards
The di-isopropyl peroxydicarbonate of correspondence ratio.
It is prepared by cathode sheets：By sulfur-graphene complex (accounting for the 95% of whole cathode-coated layer weight) and bonding agent and molten
Agent, obtains slurry after being sufficiently stirred for, afterwards process is coated, colding pressing obtains cathode sheets.
It is prepared by polymer network cathode sheets：Quality according to ethyl acrylate is the relation of the 5% of cathode quality, will
Polymer solution is uniformly sprayed on cathode sheets surface, after it fully infiltrates, pole piece is placed in 70 DEG C of environment and is toasted 4h, is made
Ethanol volatilize completely, while polymer monomer polymerization polymer network structure, it is cloudy so as to prepare polymer network
Pole piece.
It is prepared by anode strip：Graphite, conductive agent, bonding agent and solvent are sufficiently stirred for obtain anode slurry, are applied afterwards
On a current collector, Jing colding pressing, after slitting welding obtain anode strip.
It is prepared by lithium-rich anode strip：On above-mentioned anode strip top layer, layer of metal lithium band is combined, prepares lithium-rich anode strip.
It is prepared by finished product battery core：The polymer network cathode sheets, lithium-rich anode strip and the isolating membrane that prepare are wound
To naked battery core, carry out being encapsulated into bag for packaging bag using aluminum plastic film, post-drying, fluid injection, standing, chemical conversion, shaping, degasification after,
Finally give the battery core after molding.
Embodiment 1, polymer solution configuration：By nonyl tetra-acrylate：Di-isopropyl peroxydicarbonate：Ethanol=
20：0.5：79.5 ratio, stirs first standby, afterwards using first 1 by weighing nonyl tetra-acrylate, ethanol
The di-isopropyl peroxydicarbonate of correspondence ratio is added in month.
It is prepared by cathode sheets：With embodiment 1.
It is prepared by polymer network cathode sheets：Quality according to ethyl acrylate is the relation of the 5% of cathode quality, will
Polymer solution is uniformly sprayed on cathode sheets surface, after it fully infiltrates, pole piece is placed in 70 DEG C of environment and is toasted 4h, is made
Ethanol volatilize completely, while polymer monomer polymerization polymer network structure, it is cloudy so as to prepare polymer network
Pole piece.
Other are identical with embodiment 1, are not repeated herein.
Embodiment 2, as different from Example 1, the present embodiment comprises the steps：
It is prepared by polymer network cathode sheets：It is the 0.1% of cathode quality according to the quality of nonyl tetra-acrylate
Relation, polymer solution is uniformly sprayed on cathode sheets surface, after it fully infiltrates, during 70 DEG C of environment are placed in pole piece
Baking 4h so that ethanol volatilizees completely, while polymer monomer polymerization polymer network structure, so as to prepare polymerization
Thing network cathode sheets.
Other are identical with embodiment 1, are not repeated herein.
Embodiment 3, as different from Example 1, the present embodiment comprises the steps：
It is prepared by polymer network cathode sheets：It is the 0.5% of cathode quality according to the quality of nonyl tetra-acrylate
Relation, polymer solution is uniformly sprayed on cathode sheets surface, after it fully infiltrates, during 70 DEG C of environment are placed in pole piece
Baking 4h so that ethanol volatilizees completely, while polymer monomer polymerization polymer network structure, so as to prepare polymerization
Thing network cathode sheets.
Other are identical with embodiment 1, are not repeated herein.
Embodiment 4, as different from Example 1, the present embodiment comprises the steps：
It is prepared by polymer network cathode sheets：It is the 1.5% of cathode quality according to the quality of nonyl tetra-acrylate
Relation, polymer solution is uniformly sprayed on cathode sheets surface, after it fully infiltrates, during 70 DEG C of environment are placed in pole piece
Baking 4h so that ethanol volatilizees completely, while polymer monomer polymerization polymer network structure, so as to prepare polymerization
Thing network cathode sheets.
Other are identical with embodiment 1, are not repeated herein.
Embodiment 5, as different from Example 1, the present embodiment comprises the steps：
It is prepared by polymer network cathode sheets：Quality according to nonyl tetra-acrylate is the 20% of cathode quality
Relation, polymer solution is uniformly sprayed on cathode sheets surface, after it fully infiltrates, pole piece is placed in 70 DEG C of environment and is dried
Roasting 4h so that ethanol volatilizees completely, while polymer monomer polymerization polymer network structure, so as to prepare polymer
Network cathode sheets.
Other are identical with embodiment 1, are not repeated herein.
Embodiment 6, as different from Example 1, the present embodiment comprises the steps：
Polymer solution is configured：By tetramethylolmethane four (α-ethyl) acrylate：Di-isopropyl peroxydicarbonate：Acetone
=20：0.5：79.5 ratio, stirs first standby, afterwards using front 1 by weighing nonyl tetra-acrylate, ethanol
The di-isopropyl peroxydicarbonate of correspondence ratio is added in individual month.
It is prepared by polymer network cathode sheets：Quality according to tetramethylolmethane four (α-ethyl) acrylate is cathode matter
The relation of the 5% of amount, polymer solution is uniformly sprayed on cathode sheets surface, after it fully infiltrates, to pole piece 70 is placed in
4h is toasted in DEG C environment so that ethanol volatilizees completely, while polymer monomer polymerization polymer network structure, so as to prepare
Obtain polymer network cathode sheets.
Other are identical with embodiment 1, are not repeated herein.
Embodiment 7, from unlike comparative example 3, the present embodiment comprises the steps：
Polymer solution is configured：By bisphenol a dimethacrylate：Di-isopropyl peroxydicarbonate：Ethanol=20：
0.5：79.5 ratio, stirs first standby, afterwards using first 1 month by weighing nonyl tetra-acrylate, ethanol
The di-isopropyl peroxydicarbonate of interior addition correspondence ratio.
It is prepared by polymer network cathode sheets：It is the 5% of cathode quality according to the quality of bisphenol a dimethacrylate
Relation, polymer solution is uniformly sprayed on cathode sheets surface, after it fully infiltrates, during 70 DEG C of environment are placed in pole piece
Baking 4h so that ethanol volatilizees completely, while polymer monomer polymerization polymer network structure, so as to prepare polymerization
Thing network cathode sheets.
Other are identical with comparative example 3, are not repeated herein.
Embodiment 8, as different from Example 7, the present embodiment comprises the steps：
It is prepared by cathode sheets：With nano-sulfur particles and super conductive carbon composite (accounting for the 80% of cathode gross weight) and phosphorus
The mixture of sour ferrum lithium is cathode active material, adds conductive agent, bonding agent and solvent, and the moon is obtained after being sufficiently stirred for
Anode slurry, afterwards process is coated, colding pressing obtains cathode sheets.
Other are identical with comparative example 4, are not repeated herein.
The present invention is tested as follows：
Volume test：Volume test is carried out to the battery core of each embodiment and comparative example by following flow process in 35 DEG C of environment：
Stand 3min；0.5C constant-current charges are to 3.8V, constant-voltage charge to 0.05C；Stand 3min；0.5C constant-current discharges obtain head to 1.5V
Secondary discharge capacity D0；Stand and complete volume test after 3min, acquired results are shown in Table 1.
Battery core testing impedance：Battery core is charged to into 2.1V at 35 DEG C, and (charging flow is：Stand 3min；0.5C constant currents are filled
Electricity is to 2.1V, constant-voltage charge to 0.05C；Stand 3min.), test the AC impedance of battery core using electrochemical workstation afterwards, and
Test result IMP when writing scan frequency is 1000HZ, acquired results are shown in Table 1.
Loop test：Test is circulated to the battery core of each embodiment and comparative example by following flow process in 35 DEG C of environment：
Stand 3min；0.5C constant-current charges are to 3.8V, constant-voltage charge to 0.05C；Stand 3min；0.5C constant-current discharges obtain head to 1.5V
Secondary discharge capacity D0；Stand and carry out second charging after 3min：0.5C constant-current charges are to 3.8V, constant-voltage charge to 0.05C；It is quiet
Put 3min；0.5C constant-current discharges to 1.5V obtains discharge capacity D1 first；Afterwards recirculation obtains D299 298 times；Now, battery core
Capability retention=D299/D0, acquired results are shown in Table 1.
Self discharge is tested：In RT environment the battery core that each embodiment and comparative example finish loop test is entered by following flow process
Row self discharge is tested：Stand 3min；0.5C constant-current charges are to 3.0V, constant-voltage charge to 0.05C；Stand test open circuit electricity after 72h
Pressure V1, stands again afterwards 72h test open-circuit voltage V2, self-discharge rate=(V1-V2)/72 (mV/h) of battery core, acquired results
It is shown in Table 1.
Capacity, the resistance of the polymer network structure negative electrode correspondence battery core that table 1, different type of polymer and content are prepared
Anti-, cycle performance and self discharge table
Comparative examples 1 can be obtained with embodiment 1-5, and in cathode electrode, the polymer for adding the present invention prepares polymer
The lithium-sulfur cell of the lithium-sulfur cell cathode electrode that network structure is fixed, with more excellent electrical property and self-discharge performance, tool
Body shows as that capacity is slightly lifted, impedance is slightly reduced, cycle performance is significantly improved, self-discharge rate is significantly reduced；Meanwhile, when
During polymers compositionss addition excessive (20%), it will affect lithium-sulfur cell capacity to play.Comparative examples 2,3 and embodiment 6
Can obtain, addition polymer is formed after network structure cathode sheets, and the cycle performance of lithium-sulfur cell is significantly improved, but common polymer
After being added in electrode, due to impact of the polymer to lithium ion transport, the impedance of lithium-sulfur cell will be increased, affect the electricity of battery
Performance；And the introducing of polymer used in the present invention, be not in the phenomenon for reducing lithium-sulfur cell chemical property.Most
Afterwards, from embodiment 7,8 as can be seen that multiple systems of the suitable lithium-sulfur cell of the present invention.
The announcement and teaching of book according to the above description, those skilled in the art in the invention can also be to above-mentioned embodiment party
Formula is changed and changed.Therefore, above-mentioned specific embodiment is the invention is not limited in, every those skilled in the art exist
On the basis of the present invention it is done it is any conspicuously improved, replace or modification belongs to protection scope of the present invention.This
Outward, although some specific terms used in this specification, these terms merely for convenience of description, not to the present invention
Constitute any restriction.
Claims (9)
1. a kind of lithium-sulfur cell, is made up of negative electrode, anode, isolating membrane, electrolyte and outer package,
Negative electrode：It is made up of collector and overlay, the cathode active material in overlay at least contains elemental sulfur, sulfur-based compound
With the one kind in sulfur compound；The elemental sulfur includes Sublimed Sulfur and/or high purity sulphur；Sulfur-based compound include organic sulfur compound,
Li2SnIn at least one, wherein, n >=1；The sulfur compound include sulfur/carbon complex, sulfur/conductive polymer composite and
At least one in sulfur/inorganic oxide；
Anode：For lean lithium material and/or rich lithium material；The rich lithium material is lithium metal；The lean lithium material includes carbons material
At least one in material, alloy type material, metal-oxide series, metal nitride and carbon compound；
Isolating membrane：The component of function is turned on electronic isolation, ion；
Electrolyte：It is made up of lithium salts, nonaqueous solvent and additive；
Also it is distributed with derivatized polymers, and anode in cathode-coated layer and does not contain derivatized polymers；
The derivatized polymers being distributed in the cathode-coated layer include what the high polymer monomer of following structure was polymerized
Polymer：
Wherein：
R1 is linear alkyl chain, the alkyl chain containing side base or the segment containing phenyl ring；
R2 is for acrylic or containing the acrylate-based of α-side base.
2. a kind of lithium-sulfur cell described in claim 1, it is characterised in that the polymer mesh being distributed in the cathode-coated layer
Structure includes the high molecular polymer with symmetrical structure, symmetrical or axial symmetry, the height centered on the symmetrical structure
The symmetrical centre of molecule is single atom.
3. the lithium-sulfur cell described in a kind of any one of claim 1-2, it is characterised in that the high polymer monomer is selected from Ji Rensi
Alcohol tetraacrylate, season nonyl tetrol four (Alpha-Methyl) acrylate, season nonyl tetrol four (α-ethyl) acrylate, tetramethylolmethane four
Diyl is double for acrylate, tetramethylolmethane four (Alpha-Methyl) acrylate, tetramethylolmethane four (α-ethyl) acrylate, 1,6-
[oxygen (2- carboxylic propyl group -1,3- diyls)] diacrylate, bisphenol a dimethacrylate, bisphenol-A glycerol methacrylate
At least one monomer in ester is polymerized.
4. a kind of lithium-sulfur cell described in claim 1, it is characterised in that the derivatized polymers in the cathode-coated layer
In being uniformly distributed in cathode-coated layer, the quality of the polymer accounts for the 0.1%-20% of whole cathode-coated layer quality.
5. a kind of lithium-sulfur cell of claim 1, it is characterised in that the derivatized polymers in the cathode-coated layer
Form for monomer in situ polymerization.
6. the preparation method of the lithium-sulfur cell described in a kind of claim 1, it is characterised in that at least including following step：
Step 1, polymer paste configuration：High molecular component is uniformly mixed with solvent, the slurry for obtaining high molecular component is stand-by；
It is prepared by step 2, cathode electrode：By a kind of negative electrode in the complex at least containing sulphur simple substance, the compound of sulfur and sulfur
Active material, conductive agent, bonding agent and solvent mix homogeneously prepare slurry, apply obtain on a current collector negative electrode afterwards
Pole piece；
Step 3, by slurry obtained in step 1 pole piece that step 2 is obtained is sprayed at, and is permeated through fully, reacts, is removed solvent
Obtain that the cathode sheet of derivatized polymers is distributed with after change；
Step 4, the preparation of finished product lithium-sulfur cell：The cathode sheets that step 3 is obtained obtain naked electricity with anode strip, isolating membrane assembling
Core, enters afterwards shell/enter bag, baking, fluid injection, standing, chemical conversion, shaping and obtains finished product lithium-sulfur cell.
7. the preparation method of the lithium-sulfur cell described in a kind of claim 6, it is characterised in that high molecular component is described in step 1
High polymer monomer or/and high molecular polymer.
8. the preparation method of the lithium-sulfur cell described in a kind of claim 7, it is characterised in that high polymer monomer is described in step 1
High polymer monomer with symmetrical structure, including season nonyl tetra-acrylate, season nonyl tetrol four (Alpha-Methyl) acrylate, season
Nonyl tetrol four (α-ethyl) acrylate, tetramethylol methane tetraacrylate, tetramethylolmethane four (Alpha-Methyl) acrylate, Ji Wusi
Alcohol four (α-ethyl) acrylate, 1,6- diyl double [oxygen (2- carboxylic propyl group -1,3- diyls)] diacrylate, bisphenol-A diformazan
At least one in base acrylate, bisphenol-A glycerol double methyl methacrylate；High molecular polymer described in step 1 be with
The high molecular polymer of symmetrical structure.
9. the preparation method of the lithium-sulfur cell described in a kind of claim 6, it is characterised in that solvent described in step 1 include ethanol,
At least one in acetone and N-methyl ketopyrrolidine.
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| KR100497251B1 (en) * | 2003-08-20 | 2005-06-23 | 삼성에스디아이 주식회사 | Protective composition for negative electrode of lithium sulfur battery and lithium sulfur battery fabricated by using same |
| CN102142554A (en) * | 2011-02-16 | 2011-08-03 | 中国人民解放军63971部队 | Nano carbon sulfur composite material with network structure and preparation method of nano carbon composite material |
| CN103474633A (en) * | 2012-06-07 | 2013-12-25 | 中国人民解放军63971部队 | Carbon-sulfur-shell matter composite material having network dual-core shell structure and preparation method thereof |
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2015
- 2015-02-26 CN CN201510088422.3A patent/CN104659406B/en active Active
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