CN106876698A - A kind of preparation of positive material for lithium-sulfur battery and positive electrode and application - Google Patents
A kind of preparation of positive material for lithium-sulfur battery and positive electrode and application Download PDFInfo
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- CN106876698A CN106876698A CN201510918192.9A CN201510918192A CN106876698A CN 106876698 A CN106876698 A CN 106876698A CN 201510918192 A CN201510918192 A CN 201510918192A CN 106876698 A CN106876698 A CN 106876698A
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- lithium
- coordination polymer
- cladding
- lithium sulfide
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- 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
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/581—Chalcogenides or intercalation compounds thereof
- H01M4/5815—Sulfides
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- 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
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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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
- 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
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Abstract
The present invention relates to a kind of preparation method of positive material for lithium-sulfur battery, the positive electrode is to coat lithium sulfide by unlimited coordination polymer to generate cladding product, the vulcanization lithium anode material of post processing cladding product generation；It is of the invention with existing lithium-sulfur cell vulcanize lithium anode material compared with, while the suction-operated of metal, metal oxide to many lithium sulfides effectively reduces the shuttle effect of many lithium sulfides in battery system；Cladding process can effectively control the loading of lithium sulfide using dynamic process regulation and control, realize that height is supported；Process is simply easy to extensive preparation.
Description
Technical field
The present invention relates to a kind of lithium-sulfur cell body positive electrode and preparation method thereof, belong to lithium secondary battery material
Technical field.
Background technology
Trigger resource increasingly depleted, ecological pollution constantly to aggravate as energy main body using fossil, global gas
The problems such as constantly warming is waited, battery substitutes traditional fossil fuel and drives the power-equipments such as motor vehicle as science
The focus that boundary and industrial circle are paid close attention to jointly.At present, the specific capacity of lithium ion battery is close to its theoretical limit,
But it drives the mileage that electric motor car is travelled generally to be less than 100 miles as electrokinetic cell, it is impossible to meet actual
Demand.The negative pole of lithium-sulfur cell uses the lithium metal (2860mAh/g) of highest electrochemistry capacitance, positive pole to use
Sulphur can provide the reason of 1672mAh/g as active reaction thing through the electrochemical process of polysulfide generation lithium sulfide
By specific capacity.Thus, the theoretical energy density of lithium-sulfur cell can reach 2567Wh/kg, as dynamic
Power battery applications are applied to military equipment in electric motor car and one-shot battery has great potentiality.With academia and
The lasting research of industrial quarters and input, lithium-sulfur cell are widely regarded as the preferable replacer of lithium ion battery.
Positive pole as restriction lithium-sulfur cell volumetric properties and cycle life key component, by substantial amounts of research
Accumulation mainly faces following three points problem：1. active material sulphur electric conductivity is poor, causes greatly at the electric discharge initial stage
Activation polarization；2. charge and discharge process intermediate polysulfide has stronger solubility property, by shuttle to lithium
Negative terminal surface causes the reduction of volumetric properties and cycle life；3. discharge latter stage, reactant sulphur is given birth to through discharge process
Into the process of product lithium sulfide, 80% cubical expansivity causes greatly destruction to anode structure.
Using lithium sulfide as active material, it is swollen by way of first charging and discharging again can effectively to solve volume
The swollen problem for causing anode structure to destroy.At present, the preparation of vulcanization lithium electrode generally uses three kinds of methods, this
A little methods suffer from the limitation of itself：1. blending method (Cai, K.；Song,M.；Cairns,E.J.；Zhang,Y.
Nano Lett.2012,12,6474-6479.) lithium sulfide of small scale nanometer particle diameter cannot be prepared and trigger battery
High electrochemical polarization in charge and discharge process；2. synthetic method (Nan, C.Y.；Lin,Z.；Liao,H.G.；Song,M.
K.；Li,Y.D.；Cairns, E.J.J.Am.Chem.Soc.2014,136,4659-4663.) condition cannot be overcome
Harsh multistep reaction and be difficult to scale amplification；3. infusion process (Wang, C.；Wang,X.；Yang,Y.；
Kushima,A.；Chen,J.；Huang,Y.；Li, J.Nano Letters 2015,15, (3), 1796-1802.) cannot
Obtain the vulcanization lithium electrode of load amount high.Thus, how simultaneously realize vulcanize lithium electrode nanometer particle size it is controllable,
Scale is amplified and height supports the difficult point as vulcanization lithium anode material at present.
The content of the invention
High loadingses feature can be reconciled it is an object of the invention to provide a kind of active material nanometer particle size
Vulcanize lithium anode material and preparation method is easy to scale amplification.
The purpose of the present invention is achieved in the following ways.
A kind of positive electrode for lithium-sulfur cell is to coat lithium sulfide by unlimited coordination polymer to generate cladding
Product and the vulcanization lithium anode material of post processing cladding product generation.
Described unlimited coordination polymer (Infinite coordination polymers, abbreviation ICPs) refers to metal sun
The coordination polymer that ion and multiple tooth bridge ligand are formed by Coordinate self-assembly.
Described metal ion includes Zn2+, Cu2+, Ni2+, Mn2+, Au2+, Pd2+Transition metal and your gold
Category ion.
Referring to the difunctional tooth schiff bases (bis-metallo-tridentate of bimetallic three described multiple tooth bridge ligand more
Schiff's base,BMSB)。
Described cladding lithium sulfide refers to during unlimited coordination polymer coordination polymerization, by solvent-induced
Intermediate processing will vulcanize the method that lithium particle is coated in unlimited coordination polymer.
Described unlimited coordination polymer coordination polymerization process refers to multiple tooth bridge ligand and metal cation dissolving
Solution A 1 is formed in solvent orange 2 A, solution B 1, unlimited coordination polymerization are formed to solvent B is added in solution A 1
Thing particle is increasingly generated and separated out with solution B 1 and separates.
Described solvent-induced intermediate processing refers to that lithium sulfide is dissolved in solvent orange 2 A to form solution A 2, is added
The solvent B generation solution Bs 2 of insoluble lithium sulfide, lithium sulfide particle is increasingly generated and separated out with solution B 2
Separate.
The described unlimited coordination polymer that is coated on refers to that multiple tooth bridge ligand, metal cation and lithium sulfide are molten
Solution forms solution A 3 in solvent orange 2 A, and solution B 3, unlimited polycomplexation are formed to solvent B is added in solution A 3
Lithium sulfide is separated out in the presence of solvent-induced precipitation and is wrapped in unlimited polycomplexation during compound coordination polymerization
Cladding product is generated in compound.
Described solvent orange 2 A refers to the organic molten of the multiple tooth bridge ligand of high dissolution, metal cation and lithium sulfide
Agent.
Described solvent B refers to indissoluble or does not dissolve having for multiple tooth bridge ligand, metal cation and lithium sulfide
Machine solvent.
Described cladding product refers to the internal unlimited coordination polymer particle for being coated with vulcanization lithium particle.
Described vulcanization lithium particle is irregular shape particle of the diameter at 5-200 nanometers.
Described unlimited coordination polymer particle refer to 50 nanometers to 5 microns of axial distance most long nanosphere,
Nano cubic and nanometer wheel, and nano wire and nanometer rods of the diameter at 50-200 nanometers.
Described post processing refers to coat product as reactant by warm high, electrochemistry and solution heat etc.
Course of reaction.
Described high-temperature heat treatment refer to coat product in coordination polymer in 800-900 degrees Celsius of indifferent gas
Carbonization and metal cation are reduced to the process of metal under body atmosphere.
Described electrochemical treatments refer to fill out the conduction such as cladding product and CNT, Graphene, carbon fiber
Collection liquid surface is coated on after material blending, lithium sulfide, metal and conductive filler compound are generated under negative voltage
Process.
Described solution heat treatment refers to fill out the conduction such as cladding product and CNT, Graphene, carbon fiber
Material carries out reaction generation lithium sulfide, metal under heating, condition of high voltage are placed in after being well mixed by organic solvent
With the process of conductive filler compound.
Described vulcanization lithium anode material refers to the one kind or in lithium sulfide and carbon, metal, metal oxide
The compound being mutually compounded to form more than kind.
Beneficial effect of the present invention
The present invention obtains vulcanizing the excellent of lithium anode material by the way that unlimited coordination polymer cladding lithium sulfide is post-treated
Point is to select the unlimited coordination polymer for being easy to regulate and control polymerization process by solvent-induced method to be used as cladding
Agent, can control cladding process using number of ways.Meanwhile, solvent-induced method is also applied for lithium sulfide grain
The precipitation of son, the precipitation and unlimited coordination polymer polymerization process for realizing lithium sulfide is synchronously carried out, effectively control
Vulcanize the particle diameter of lithium particle.Secondly, unlimited coordination polymer serves not only as covering can also be used as presoma
The post-treated material for obtaining the high conductivity such as carbon, metal and metal oxide and adsorptivity, improves battery
Overall performance.Finally, the abundant structure of unlimited coordination polymer, yardstick and shape are changed into further optimization vulcanization
Lithium anode material provides good approach.
It is of the invention with existing lithium-sulfur cell vulcanize lithium anode material compared with, have the following advantages that：First, sulphur
The particle diameter for changing lithium can be by the addition of the concentration of metal cation, part and lithium sulfide and different solvents speed
Degree regulation, the work of its electrochemistry can be effectively improved the characteristics of the nanoscale lithium sulfide of preparation has high-ratio surface
Property；Second, lithium sulfide effectively overcomes lithium sulfide electrical conductivity not enough in being coated on carbon, metal, metal oxide
Shortcoming, while the suction-operated of metal and metal oxide to many lithium sulfides effectively reduces many in battery system
The shuttle effect of lithium sulfide；Third, cladding process can effectively control lithium sulfide using dynamic process regulation and control
Loading, realize that height is supported；Fourth, the liquid phase blending used in vulcanization lithium anode material preparation process,
The industrialization that the methods such as precipitate and separate, high temperature cabonization, electrochemical treatments, high pressure thermal response are maturation is advised greatly
The mould means of production, while this process only needs three to four-step reaction, process is simply easy to extensive preparation.
Specific embodiment
Below by embodiment and comparative example, the invention will be further described, rather than the limitation present invention.
Embodiment 1
Take 1.0g4- carbamoyl benzoates and 1.1g 4- amino-3-hydroxy formic acid is dissolved separately in 20mL dimethyl
It is to be dissolved to be transferred in flask completely in sulfoxide, 90 degrees Celsius of back flow reaction 30min.Black precipitate is taken, is gone
Ionized water rinses suction filtration removal salt ion.Cleaned three times through dimethyl sulfoxide (DMSO), subsequent 60 degrees Celsius of vacuum drying.
Under an argon atmosphere, take black precipitate 60mg and zinc acetate 100mg and be dissolved in the anhydrous second of 10mL
In alcohol, take 60mg lithium sulfides and be dissolved in 10mL ethanol, two kinds of solution are well mixed stand-by.To mixed
The ether solvent of 10mL is slowly added dropwise in conjunction liquid, normal temperature stands 30min.Extracting yellow is precipitated, using a small amount of
After ethanol solution drip washing yellow mercury oxide, room temperature in vacuo dries 4-8h.
0.02mol palladiums are dissolved in 1mL dimethylformamides, it is to be dissolved completely to palladium solution
The middle addition above-mentioned yellow mercury oxides of 12mg, by mixed liquor strength vibration 2h.Brown precipitate is taken, using diformazan
Base formamide cyclic washing.
Take the above-mentioned brown precipitates of 5mg and 1mg SWCNs be scattered in 20mL dimethylformamides,
Strong stirring 2h.Brownish black sediment is taken, is cleaned repeatedly using dimethylformamide, be vacuum dried 4-8h.
Above-mentioned brownish black sediment 2mg ultrasonic disperses are taken in 2mLN- methyl pyrrolidones, viscous fluid is coated
In foam nickel surface, 45 degrees Celsius dry 12h.To be carried on the dark brown color substance of nickel foam as work electricity
Pole, used as to electrode, Ag/AgCl is used as to electrode, and the BMImBF4 of 0.5mol/L H2SO4 is molten for platinum filament
Liquid runs 10min generations, the positive electrode of Li2S/Pd/SWNT compounds as electrolyte under -0.2V.
Claims (7)
1. a kind of preparation method of positive material for lithium-sulfur battery, it is characterised in that：The positive electrode is logical
Unlimited coordination polymer cladding lithium sulfide generation cladding product is crossed, the lithium sulfide of post processing cladding product generation is just
Pole material；Described unlimited coordination polymer refers to metal cation and multiple tooth bridge ligand by coordination from group
The coordination polymer for filling and being formed；Described metal ion includes Zn2+、Cu2+、Ni2+、Mn2+、Au2+Or Pd2+
In one or more；Multiple tooth bridge ligand is the tooth schiff bases of bimetallic three；Wherein in coordination polymer
Metal cation is 1 with the mol ratio of multiple tooth bridge ligand：1-1：5, the molecular weight of coordination polymer is
103-105；
Described cladding lithium sulfide refers to during unlimited coordination polymer coordination polymerization, by solvent-induced heavy
Shallow lake method is coated on lithium particle is vulcanized in unlimited coordination polymer；
The process of the generation cladding product is that unlimited coordination polymer and lithium sulfide are dissolved in into solvent orange 2 A forms
Solution A 1, solution B 1, unlimited coordination polymer coordination polymerization process are formed to solvent B is added in solution A 1
Middle lithium sulfide is separated out in the presence of solvent-induced precipitation and is wrapped in generation cladding product in unlimited coordination polymer
Thing；The mass concentration of unlimited coordination polymer is 1-10%, and the mass concentration of lithium sulfide is 1-10%, described
Solvent orange 2 A is the one kind in carbon disulfide, absolute ethyl alcohol, poly phosphoric sulfide, polyethylene glycol；
Described solvent B is in organic solvent ether, propyl ether, butyl ether, ethyl acetate, acetone, chloroform
Kind；
Described cladding product refers to the internal unlimited coordination polymer particle for being coated with vulcanization lithium particle.
2. according to the preparation method described in claim 1, it is characterised in that：
Described vulcanization lithium particle is irregular shape particle of the diameter at 5-200 nanometers；
Described unlimited coordination polymer particle refer to the nanosphere of axial distance 50-200nm most long, nanometer stand
One or two or more kinds of side or/and nanometer wheel, diameter in 50-200 nanometers of nano wire or/and nanometer rods.
3. according to the preparation method described in claim 1, it is characterised in that：
Described post processing refers to coat product as reactant by warm high, electrochemistry or solution heat treatment
Process；
Described warm high refers to that cladding product is carbonized under 800-900 degrees Celsius of inert atmosphere；
Described electrochemical treatments refer to by cladding product and one kind or two in CNT, Graphene or carbon fiber
The blending of above conductive filler is planted, the mass content of conductive filler is 3~15%, is coated after mixing with organic solvent
In collection liquid surface, in 1.5~2.1V (vs.Li/Li+) under to generate lithium sulfide, metal and conductive filler multiple
The process of compound；Organic solvent quality is coat product and conductive filler sum 3~10 times；
Described solution heat treatment refers to by cladding product and one kind or two in CNT, Graphene or carbon fiber
The conductive filler blending of the above is planted, is dissolved in organic solvent, under 150-180 degrees Celsius, 2~10MPa
Carry out the process of reaction generation lithium sulfide, metal and conductive filler compound；The quality of wherein conductive filler contains
It is 3%~15% to measure, and organic solvent quality is coat product and conductive filler sum 3~10 times.
4. according to the preparation method described in claim 3, it is characterised in that：Organic solvent be DMAC, DMF,
One kind in DMSO, NMP.
5. the positive electrode of any preparations of a kind of claim 1-4.
6. according to the positive electrode described in claim 5, it is characterised in that：
Described vulcanization lithium anode material refers to that lithium sulfide, carbon material and metal or metal oxide are compounded to form
Compound.
7. positive electrode described in a kind of claim 5 is applied in lithium-sulfur cell.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019095355A1 (en) * | 2017-11-20 | 2019-05-23 | 迪吉亚节能科技股份有限公司 | Preparation method of composite material containing sulfur-containing conductive polymer |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101719545A (en) * | 2009-12-16 | 2010-06-02 | 北京理工大学 | Anode composite material of lithium sulfur battery and preparation method thereof |
| 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 |
| CN103208618A (en) * | 2013-04-24 | 2013-07-17 | 中国科学院苏州纳米技术与纳米仿生研究所 | Carbon-sulfur composite positive electrode material of lithium-ion battery and preparation method of material |
| CN104882601A (en) * | 2014-02-05 | 2015-09-02 | 通用汽车环球科技运作有限责任公司 | Sulfur Based Active Material For A Positive Electrode |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101719545A (en) * | 2009-12-16 | 2010-06-02 | 北京理工大学 | Anode composite material of lithium sulfur battery and preparation method thereof |
| 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 |
| CN103208618A (en) * | 2013-04-24 | 2013-07-17 | 中国科学院苏州纳米技术与纳米仿生研究所 | Carbon-sulfur composite positive electrode material of lithium-ion battery and preparation method of material |
| CN104882601A (en) * | 2014-02-05 | 2015-09-02 | 通用汽车环球科技运作有限责任公司 | Sulfur Based Active Material For A Positive Electrode |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019095355A1 (en) * | 2017-11-20 | 2019-05-23 | 迪吉亚节能科技股份有限公司 | Preparation method of composite material containing sulfur-containing conductive polymer |
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