CN106252722A - A kind of additive with dual Li dendrite inhibitory action and application thereof - Google Patents

A kind of additive with dual Li dendrite inhibitory action and application thereof Download PDF

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Publication number
CN106252722A
CN106252722A CN201610649434.3A CN201610649434A CN106252722A CN 106252722 A CN106252722 A CN 106252722A CN 201610649434 A CN201610649434 A CN 201610649434A CN 106252722 A CN106252722 A CN 106252722A
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electrolyte
additive
battery
dendrite
lithium
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项宏发
谢勇
梁栋栋
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Hefei University of Technology
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Hefei University of Technology
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Priority to CN201910633516.2A priority Critical patent/CN110444813B/en
Priority to CN201610649434.3A priority patent/CN106252722A/en
Publication of CN106252722A publication Critical patent/CN106252722A/en
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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
    • 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
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0567—Liquid materials characterised by the additives
    • 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
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Abstract

The invention discloses a kind of additive with the formation of double inhibition Li dendrite and application thereof, and containing the electrolyte of examples of such additives, battery and preparation method thereof.Described additive is a kind of typical nonionic surfactant, and additive mass fraction in the electrolyte is 0.05%～5%.The present invention is by adding the simple approach of a kind of organic additive in the electrolyte, inhibit Li dendrite in the formation of electrode surface in terms of two: 1) improve the wellability of electrolyte and barrier film by reducing electrolyte surface tension force, increase lithium ion transmission channel in barrier film, so that lithium ion stream is uniformly distributed at electrode surface is finally reached the purpose that suppression Li dendrite is formed；2) additive is by improving the lithium ion deposition site at electrode surface further in electrode surface absorption, thus suppresses Li dendrite to be formed.Safety and the cycle performance of lithium secondary battery will be greatly improved by adding this additive in the electrolytic solution.

Description

A kind of additive with dual Li dendrite inhibitory action and application thereof
Technical field
The invention belongs to cell art, particularly to a kind of lithium secondary battery with dual Li dendrite inhibitory action Electrolyte organic additive and the application in preparing electrolyte thereof.
Background technology
Energy crisis and environmental pollution are two hang-ups that current social faces.Non-renewable due to fossil energy, People have to sight to invest some novel regenerative resources, such as wind energy, tide energy, biomass energy etc..But, due to this The property the most quietly of a little novel energies is with intermittent, it is desirable to improve its utilization rate and a kind of energy density must be used high, safety and stability These energy storages are first got up and discharge the most smoothly by the energy storage device that property is good.City environmental pollution problem is the most prominent Going out, wherein most provides from fuel-engined vehicle exhaust emissions, the discharge appearing as solving vehicle exhaust of electric automobile Solution.But but electrokinetic cell is to hinder the big bottleneck of electric automobile wide variety of.Currently, be widely used in portable Lithium ion battery in formula electronic product is considered as the prioritizing selection of energy storage and electrical source of power.But its energy density can't Fully meet the demand of energy storage and electric automobile.A new generation has the Novel energy storage apparatus of high-energy-density in the urgent need to being developed Out.
Lithium metal is owing to having specific capacity big (3860mAh/g), and oxidation-reduction potential low (-3.04V vs SHE) etc. is Row advantage is always treated as a kind of preferably cell negative electrode material.If the graphite cathode in existing lithium-ion battery system is used Lithium an-ode substitutes, then the energy density of whole battery will be greatly improved.In addition, lithium metal is as negative Pole material is given great expectations especially and is applied in a new generation's high energy density cells, such as Li-S, Li-O2Deng.
But, lithium metal easily produces dendrite as negative pole in cyclic process, causes potential safety hazard.So while have Series of advantages, the road of the commercialization of lithium an-ode walks abnormal slow.The operation principle of abjection is embedded not with graphite electrode With, lithium ion is a simple oxidation-reduction process in lithium metal surface.Due to the abjection that lithium ion is the most uneven And deposition so that there is a kind of preferential growth phenomenon in lithium sheet surface, thus produces dendritic lithium metal dendrite.Due in circulation During the continuous growth of Li dendrite, it very likely pierces through barrier film and arrives positive pole and cause the short circuit of inside battery both positive and negative polarity, causes Hot-spot causes fire even to explode, so that battery based on lithium an-ode has the biggest potential safety hazard.So, solve Certainly the dendrite problems in lithium an-ode cyclic process becomes a major challenge of present battery research field.Additionally, with graphite be , at low temperature or in the case of filling soon, the most easily there is Li dendrite on graphite cathode surface in the lithium ion battery of negative pole.Thus, suppress lithium The formation of dendrite and growth are the problems that lithium secondary battery application is urgently to be resolved hurrily with evolution.
Currently, the method for suppression Li dendrite is a lot, as proposed to use the method for sputtering at lithium table in patent CN1508893A Face forms one layer of Li3PO4, then lead to N2LIPON protective layer is formed, the way suppression Li dendrite suppressed by machinery on lithium surface Formation.Additionally exploitation Novel lithium secondary cell electrolysis plastidome is also a general orientation of suppression Li dendrite, such as patent CN103531839A proposes a kind of novel high concentration lithium salts electrolyte system anti-to alleviate between electrolyte and lithium metal And Li dendrite should be suppressed.In addition, the way of the collector of a kind of 3D of patent CN103384000A ingehious design improves Lithium secondary battery performance, by making electrode in the skeleton of the lithium metal a kind of 3D of having structure of injection, this electrode will be big Reduce the local current densities of electrode greatly thus reach the effect of dendrite inhibition.To sum up, it is found that These methods, while can Improve lithium ion to a certain extent in electrode surface deposition morphology, but owing to operating process is loaded down with trivial details, be not appropriate for extensive Commodity production.Use by contrast in the electrolytic solution add additive way improve or solve Li dendrite problem be then one just Victory mode effectively.The most current overwhelming majority additive all forms SEI film by participation and improves or dendrite inhibition Being formed, this kind of additive often lost efficacy gradually along with the increase of cycle-index.Further, this kind of additive often acts on single Not can solve dendrite problems.Here, it is proposed that a kind of novel lithium two with dual Li dendrite inhibitory action Primary cell electrolysis additive, its action principle is in the distribution of electrode surface and to improve lithium ion and exist by improving lithium ion stream The dual function of the deposition site of electrode surface suppresses Li dendrite in the formation of electrode surface, efficiently solves current techniques The problem existed.
Summary of the invention
It is an object of the invention to overcome the deficiencies in the prior art, it is provided that a kind of have adding of dual Li dendrite inhibitory action Adding agent and application thereof, to solve the problem that in lithium battery, Li dendrite is formed and grows up, the present invention can effectively prevent lithium ion at electricity Surface, pole deposition produces dendrite, thus safety of lithium secondary battery is greatly improved.
The invention provides the additive of a kind of electrolyte with dual Li dendrite inhibitory action, the chemistry of additive leads to Formula is ABA or AB, wherein,
A is hydrophilic functional groups, selected from polyethylene glycol oxide HO-(CH2-CH2-O)n-H or polyhydric alcohol CnH2n+2-x(OH)xIn one Kind, wherein x >=3；
B is hydrophilic functional groups, selected from polypropylene oxide HO-(CH (CH3)-CH2-O)n-H, alkyl phenol CnH2n-1C6H5, straight One in chain alkylene or branched hydrocarbyl.
Further, in order to preferably suppress formation and the growth of Li dendrite, additive is:
HO-CH2-CH2-(O-CH2-CH2)98-(O-CH(CH3)-CH2)67-(O-CH2-CH2)98-CH2-CH2-OH、HO-CH2- CH2-(O-CH2-CH2)33-(O-CH(CH3)-CH2)35-(O-CH2-CH2)33-CH2-CH2-OH、C6H11C6H4-(O-CH2-CH2)20- CH2-CH2-OH、C6H11C6H4-C9H13(OH)4、C30H61-C9H13(OH)4、C15H29C6H4-C9H13(OH)4、C7H13C6H4-(O-CH2- CH2)45-CH2-CH2-OH、HO-CH2-CH2-(O-CH2-CH2)13-(O-CH(CH3)-CH2)45-(O-CH2-CH2)13-CH2-CH2- OH, C10H21-O-(CH2-CH2-O)13-CH2-CH2-OH or C15H29-C6H4-O-C4H9In one.
Further, this additive is joined electrolyte can be prepared the electrolysis with dual Li dendrite inhibitory action Liquid, this additive can be applicable in the preparation of electrolyte.
Add containing serving following effect after the arbitrary additive in above-mentioned formula in the electrolytic solution, first: Neng Gouyou Effect reduces the surface tension of electrolyte, and one direct result of the reduction of electrolyte surface tension force is exactly that the wellability with barrier film becomes Good, enable electrolyte to penetrate into greatest extent inside barrier film with the good wellability of barrier film and go, thus be the biography of lithium ion The more passage of defeated offer, just because of the increase of lithium ion transport passage in barrier film make lithium ion stream electrode surface point Cloth is more uniform, effectively prevent the lithium ion Local enrichment at electrode surface, greatly reduces the risk that Li dendrite produces；The Two, owing to surfactant has stronger adsorption so that it can be attached to electrode surface by absorption, due to electrode Surface irregularity, the position absorption surface activating agent protruded often is less, and sunk place is adsorbed more, this Plant selective absorption and can effectively improve the lithium ion deposition site at electrode surface, play the work of leveling electrode surface With, because needing the energy barrier crossed the biggest when the local lithium ion that SURFACTANT ADSORPTION is much reduces at this, thus suppress lithium Dendrite produces.By using this electrolyte can be effectively improved the lithium ion deposition morphology at electrode surface, extend the circulation of battery In the life-span, reduce the security risk of lithium battery.
Further, above-mentioned additive can be joined the formation carrying out double inhibition Li dendrite in electrolyte and becomes Long.
Further, there is the preparation method of the electrolyte of dual Li dendrite inhibitory action, including following preparation process:
1) weighing lithium salts and be dissolved in organic solvent, compound concentration is the solution of 1mol/L, and left at room temperature three days is standby With；
2) additive is dissolved in step 1) in the solution that obtains, i.e. obtain electrolyte, the matter of additive in electrolyte Amount mark is 0.05%～5%.
Further, the one during the lithium salts in electrolyte can be inorganic lithium salt or organic lithium salt.Inorganic lithium salt is LiPF6、LiBF4、LiClO4、LiAsF6、LiNO3、LiI、LiCl、LiBr、LiCF3SO3Or LiC4F9SO3In one；Organolithium Salt is LiN (CxF2x+1SO2)(CyF2y+1SO2)、LiC(SO2CF3)3、LiPFa(CF3)6-aOr LiPFb(C2F5)6-bIn one, its Middle x, y, a, b are natural number, a, b≤6；
Further, selected in electrolyte organic solvent can be Allyl carbonate (PC), ethylene carbonate (EC), Dimethyl carbonate (DMC), diethyl carbonate (DEC), Ethyl methyl carbonate (EMC), gamma butyrolactone (γ BL), oxolane (THF), 1,3 dioxolanes (DOL), dimethoxymethane (DMM), 1,2 dimethoxy-ethanes (DME) or tetraethyleneglycol dimethyl ether (TEGDME) one or more mixed liquors in.
Further, use and there is battery prepared by the electrolyte of dual Li dendrite inhibitory action, also include battery case, electricity Pond positive pole, battery cathode and barrier film, battery cathode is arranged on the negative pole district of described battery case, and anode is arranged on described battery The positive polar region of shell, positive polar region and negative pole district are provided with the electrolyte containing above-mentioned additive, positive polar region and negative pole district by every Film separates, and is then sealed by battery case.
Further, the material that anode is selected is cobalt acid lithium (LiCoO2), LiMn2O4 (LiMn2O4), lithium nickelate (LiNiO2), LiFePO4 (LiFePO4), CNT and sulfur composite, hollow carbon and sulfur composite, mesoporous carbon and sulfur Composite, activated carbon and sulfur composite, graphite and sulfur composite, Graphene and sulfur composite, metal-oxide, gold Belonging to the one or more combination in nitride or Carbon Materials, the material that battery cathode is selected is lithium metal or graphite electrode, barrier film Use in polyethylene (PE), polypropylene (PP) or polyethylene-polypropylene-polyethylene composite diaphragm (PE-PP-PE) Kind, the model of battery case is CR2032 button battery shell, it is also possible to being the battery of other forms, the principle of employing is identical all Can.
A kind of additive with dual Li dendrite inhibitory action disclosed by the invention and application thereof, and add containing above-mentioned Electrolyte adding agent and preparation method thereof, compared with prior art the present invention has the following advantages and improves: (one), is different from biography System electrolysis additive suppresses the action principle of Li dendrite by participating in forming SEI film, and in the present invention, electrolyte is to lithium branch Brilliant suppression is then from the ultimate principle improving lithium ion deposition, fundamentally solves the generation of Li dendrite, compared to front A kind of mode, the advantages such as it is high that the present invention has reliability, and action effect is lasting；(2) in the method for, traditional suppression Li dendrite Its action principle is the most single, DeGrain, and the electrolyte in the present invention has the both inhibitory effects to Li dendrite, energy Enough well overcome the unconspicuous problem of Li dendrite inhibition in traditional method.
Accompanying drawing explanation
Fig. 1 is embodiment 1,2,3,4 and comparative example 1 septation absorbance comparison diagram；
Fig. 2 is electrolyte and membrane contacts angle comparison diagram in comparative example 1 (a) and embodiment 1 (b)；
Fig. 3 is comparative example 1, Li in embodiment 1 and embodiment 2 | | the volt-time curve figure of Cu battery；
Fig. 4 is the SEM figure of copper foil surface lithium ion deposition morphology in comparative example 1；
Fig. 5 is the SEM figure of copper foil surface lithium ion deposition morphology in embodiment 1；
Fig. 6 is embodiment 1 and comparative example 1 battery capacity attenuation verses.
Detailed description of the invention
Elaborating embodiments of the invention below, the present embodiment is carried out under premised on technical solution of the present invention Implement, give detailed embodiment and concrete operating process, but protection scope of the present invention is not limited to following enforcement Example.
Embodiment 1
1) electrolyte configuration
The first step, precise 1.177g lithium hexafluoro phosphate (LiPF6), it is dissolved in 8.823g Allyl carbonate (PC) solution It is configured to 1M LiPF6/ PC electrolyte；Second step, precise 0.01g additive HO-CH2-CH2-(O-CH2-CH2)98-(O- CH(CH3)-CH2)67-(O-CH2-CH2)98-CH2-CH2-OH, is dissolved in 4.99g 1M LiPF6In/PC, obtain additive quality and divide Number is the electrolyte of 0.2%.Stand three days standby.Above step all complete in glove box (water oxygen content be respectively less than 0.1ppm)。
2) electrolyte is tested with barrier film wellability
Electrolyte surface tension test: use surface tension instrument test electrolyte surface tension force
Barrier film pick up is tested: the first step, and polyethylene (PE) barrier film is fabricated to the sequin of a diameter of 16mm；Second Step, takes a small amount of 1 with centrifuge tube) in electrolyte, then the PE barrier film sequin prepared 5 is immersed 2 hours；3rd step, Weigh, first with filter paper, the electrolyte of membrane surface is dried, then weigh with scale；4th step: calculate with reference to below equation and inhale Liquid rate:
In formula, M0For barrier film initial mass, M is the quality of absorbed electrolyte metacneme.Final pick up take five parallel The meansigma methods of experiment.
Contact angle is tested: use contact angle instrument test PE barrier film and electrolyte contacts angle.
3) barrier film electrical conductivity test
Testing procedure: first the PE barrier film of diameter 16mm is immersed electrolyte 2 hours, then with two panels stainless steel substrates clamp every Film and on electrochemical workstation Impedance measurement (frequency range 1～100kHZ)；Take the point that intersects with abscissa in spectrogram for every Film internal resistance, is designated as Rb.According to below equation calculating barrier film electrical conductivity:
Wherein, d is membrane thicknesses, and A is diaphragm area.
4) battery assembles and test
Battery assemble: assemble Li | | Cu CR2032 button cell investigate additive electrode surface adsorption and Lithium ion is in electrode surface deposition morphology.Wherein positive pole uses Copper Foil, and barrier film uses PE, and negative pole uses lithium sheet, and electrolyte is 1) Middle electrolyte.Assemble Li | | LiFePO4The test additive impact on cycle performance of battery of CR2032 button cell.Wherein positive pole Use commercialization LiFePO4, active material, conductive agent, the ratio of binding agent is 8:1:1, and barrier film uses PE, and electrolyte is 1) in Electrolyte, negative pole is lithium metal.It is all to carry out (water oxygen content is respectively less than 0.1ppm) in glove box that battery assembles.
Battery testing: use Arbin BT2000 test system that battery is tested.Wherein Li | | Cu CR2032 button Battery is with 0.1mA/cm2Discharge 15 hours, investigate cell voltage time graph, and copper foil surface lithium metal deposit pattern.Li| |LiFePO4CR2032 button cell is first with 0.1C activation two circle, then with 1C (～1mA/cm2) current cycle 100 encloses, and investigates battery Capacity attenuation.
5) electrode surface SEM test
Li by electric discharge 15h | | Cu CR2032 battery is taken apart in glove box, cleans Copper Foil by dimethyl carbonate (DMC) Surface, then processes its evacuation in glove box transfer chamber so that it is the DMC on surface volatilizees completely.Then with special close Electrode slice is transferred to observe in SEM by envelope container.Li by circulation 100 circle | | LiFePO4CR2032 battery is torn open in glove box Open, clean copper foil surface by dimethyl carbonate (DMC), then its evacuation in glove box transfer chamber is processed so that it is surface DMC volatilize completely.Then transfer to SEM observes by electrode slice with special sealing container.
Embodiment 2
Electrolyte configures
The first step, precise 1.177g lithium hexafluoro phosphate (LiPF6) it is dissolved in preparation in 8.823g Allyl carbonate (PC) Become 1M LiPF6/ PC electrolyte；Second step, with precise 0.025g additive HO-CH in glove box2-CH2-(O-CH2- CH2)98-(O-CH(CH3)-CH2)67-(O-CH2-CH2)98-CH2-CH2-OH, is dissolved in 4.975g 1M LiPF6In/PC, added Add the electrolyte that agent mass fraction is 0.5%.Stand three days standby.
Remaining step is similar to Example 1.
Embodiment 3
Electrolyte configures
The first step, precise 1.177g lithium hexafluoro phosphate (LiPF6) it is dissolved in preparation in 8.823g Allyl carbonate (PC) Become 1M LiPF6/ PC electrolyte；Second step, with balance precise 0.05g additive HO-CH in glove box2-CH2-(O- CH2-CH2)98-(O-CH(CH3)-CH2)67-(O-CH2-CH2)98-CH2-CH2-OH, is dissolved in 4.95g 1M LiPF6In/PC, obtain Additive mass fraction is the electrolyte of 1%.Stand three days standby.
Remaining step is similar to Example 1.
Embodiment 4
Electrolyte configures
The first step, precise 1.177g lithium hexafluoro phosphate (LiPF6) it is dissolved in preparation in 8.823g Allyl carbonate (PC) Become 1M LiPF6/ PC electrolyte；Second step, with balance precise 0.1g additive HO-CH in glove box2-CH2-(O- CH2-CH2)98-(O-CH(CH3)-CH2)67-(O-CH2-CH2)98-CH2-CH2-OH, is dissolved in 4.9g 1M LiPF6In/PC, obtain Additive mass fraction is the electrolyte of 2%.Stand three days standby.
Remaining step is similar to Example 1.
Embodiment 5
Electrolyte configures
The first step, precise 1.177g lithium hexafluoro phosphate (LiPF6), it is dissolved in 8.823g Allyl carbonate (PC) solution It is configured to 1M LiPF6/ PC electrolyte；Second step, precise 0.05g additive HO-CH2-CH2-(O-CH2-CH2)33-(O- CH(CH3)-CH2)35-(O-CH2-CH2)33-CH2-CH2-OH, is dissolved in 4.95g 1M LiPF6In/PC, obtain additive quality and divide Number is the electrolyte of 1%.Stand three days standby.Above step all completes (water oxygen content is respectively less than 0.1ppm) in glove box.
Remaining step is similar to Example 1.
Embodiment 6
Electrolyte configures
The first step, with lithium hexafluoro phosphate (LiPF6) it is lithium salts, ethylene carbonate (EC) and dimethyl carbonate (DMC) mixing Liquid (volume ratio is 1:1) is that 1M LiPF prepared by solvent6/ EC+DMC electrolyte；Second step is accurate with balance in glove box Weigh 0.075g addition of C6H11C6H4-(O-CH2-CH2)20-CH2-CH2-OH, is dissolved in 4.925g 1M LiPF6In/PC, obtain Additive mass fraction is the electrolyte of 1.5%.Stand three days standby.
Remaining step is similar to Example 1.
Embodiment 7
Electrolyte configures
The first step, with LiPF2(C2F5)4For lithium salts, ethylene carbonate (EC) and dimethyl carbonate (DMC) mixing liquid (body Long-pending ratio is 1:1) it is that 1MLiPF prepared by solvent2(C2F5)4/ EC+DMC electrolyte；Second step, accurately claims with balance in glove box Amount 0.01g addition of C6H11C6H4-C9H15(OH)4, it is dissolved in 4.99g 1M LiPF2(C2F5)4In/EC+DMC electrolyte, added Add the electrolyte that agent mass fraction is 0.2%.Stand three days standby.
Remaining step is similar to Example 1.
Embodiment 8
Electrolyte configures
The first step, with double trifluoromethanesulfonimide lithiums (LiTFSI) as lithium salts, Allyl carbonate (PC) is solvent preparation 1M LiTFSI/PC electrolyte；Second step, precise 0.25g additive HO-CH2-CH2-(O-CH2-CH2)98-(O-CH (CH3)-CH2)67-(O-CH2-CH2)98-CH2-CH2-OH, is dissolved in 4.75g 1M LiTFSI/PC, obtains additive quality and divides Number is the electrolyte of 5%.Stand three days standby.Above step all completes (water oxygen content is respectively less than 0.1ppm) in glove box.
Remaining step is similar to Example 1.
Embodiment 9
Electrolyte configures
The first step, with LiBF4 (LiBF4) it is lithium salts, Allyl carbonate (PC) is that 1M LiBF prepared by solvent4/ PC electricity Solve liquid；Second step, precise 0.01 additive HO-CH2-CH2-(O-CH2-CH2)98-(O-CH(CH3)-CH2)67-(O-CH2- CH2)98-CH2-CH2-OH, is dissolved in 9.99g 1M LiBF4In/PC, obtain the electrolyte that additive mass fraction is 0.1%. Stand three days standby.Above step all completes (water oxygen content is respectively less than 0.1ppm) in glove box.
Remaining step is similar to Example 1.
Embodiment 10
Electrolyte configures
The first step, with hexafluoroarsenate lithium (LiAsF6) it is lithium salts, Allyl carbonate (PC) is that 1M LiAsF prepared by solvent6/PC Electrolyte；Second step, precise 0.01g additive HO-CH2-CH2-(O-CH2-CH2)98-(O-CH(CH3)-CH2)67-(O- CH2-CH2)98-CH2-CH2-OH, is dissolved in 4.99g 1M LiAsF6In/PC, obtain the electrolysis that additive mass fraction is 0.2% Liquid.Stand three days standby.Above step all completes (water oxygen content is respectively less than 0.1ppm) in glove box.
Remaining step is similar to Example 1.
Embodiment 11
Electrolyte configures
The first step, with lithium hexafluoro phosphate (LiPF6) it is lithium salts, with Allyl carbonate (PC) and 1,2 dimethoxy-ethanes (DME) mixing liquid (volume ratio is 1:1) is that 1M LiPF prepared by solvent6/ PC+DME electrolyte；Second step, uses in glove box Balance precise 0.01g additive HO-CH2-CH2-(O-CH2-CH2)98-(O-CH(CH3)-CH2)67-(O-CH2-CH2)98- CH2-CH2-OH, is dissolved in 19.99g 1M LiPF6In/PC+DME electrolyte, obtain the electrolysis that additive mass fraction is 0.05% Liquid.Stand three days standby.
Remaining step is similar to Example 1.
Embodiment 12
Electrolyte configures
The first step, LiPF6For lithium salts, (volume ratio is to mix liquid with ethylene carbonate (EC) and diethyl carbonate (DEC) It is 1:1) that 1M LiPF prepared by solvent6/ EC+DEC electrolyte；Second step, adds with balance precise 0.01g in glove box Agent HO-CH2-CH2-(O-CH2-CH2)98-(O-CH(CH3)-CH2)67-(O-CH2-CH2)98-CH2-CH2-OH, is dissolved in 4.99g 1M LiPF6In/EC+DEC, obtain the electrolyte that additive mass fraction is 0.2%.Stand three days standby.
Remaining step is similar to Example 1.
Embodiment 13
Electrolyte configures
The first step, with LiTFSI as lithium salts, with 1,3 dioxolanes (DOL) and 1,2 dimethoxy-ethanes (DME) mix Liquid (volume ratio is 1:1) is that 1M LiTFSI/DOL+DME electrolyte prepared by solvent；Second step, accurate with balance in glove box Really weigh 0.25g additive HO-CH2-CH2-(O-CH2-CH2)98-(O-CH(CH3)-CH2)67-(O-CH2-CH2)98-CH2-CH2- OH, is dissolved in 4.75g 1M LiTFSI/DOL+DME, obtains the electrolyte that additive mass fraction is 5%.Stand three days standby With.
Remaining step is similar to Example 1.
Embodiment 14
Polypropylene (PP) barrier film, remaining step is used in electrolyte assembles with the test of barrier film wellability and battery and tests Similar with embodiment 1.
Embodiment 15
Polyethylene-polypropylene-polyethylene is used in electrolyte assembles with the test of barrier film wellability and battery and tests (PE-PP-PE) composite diaphragm, remaining step is similar with embodiment 1.
Embodiment 16
Battery assembles and test
Assemble Li | | LiCoO2The test of CR2032 button cell is containing additive electrolyte (embodiment 1) cycle performance of battery. Wherein positive pole uses commercialization LiCoO2, active material, conductive agent, the ratio of binding agent is 84:8:8, and barrier film uses PE, electrolysis Liquid is electrolyte in embodiment 1, and negative pole is lithium metal.Battery assemble be all carry out in glove box (water oxygen content be respectively less than 0.1ppm)。
Remaining step is similar to Example 1.
Embodiment 17
1) battery assembles and test
Battery assembles: assemble Li | | graphite half-cell, investigate additive and lithium ion is deposited at graphite electrode surface With embed the impact of pattern and the additive adsorption at graphite surface.Wherein graphite is commercialization graphite, electrode fabrication Middle graphite is 92:8 with the ratio of binding agent, and battery diaphragm uses PE, and electrolyte uses electrolyte in embodiment 12.Assemble graphite||LiFePO4Cycle performance of battery investigated by CR2032 button cell.Wherein positive electrode uses commodity LiFePO4.Electricity Active material in the making of pole, conductive agent, the ratio of binding agent is 8:1:1.Barrier film uses PE.Electrolyte is to be electrolysed in embodiment 12 Liquid.Negative pole is commercialization graphite, and in electrode fabrication, graphite is 92:8 with the ratio of binding agent.
Battery testing: use Arbin BT2000 test system that battery is tested.Wherein Li | | graphite CR2032 button cell is with 0.1mA/cm2Discharge 15 hours, investigate cell voltage time graph, and graphite surface lithium metal sinks Long-pending pattern.graphite||LiFePO4CR2032 button cell is first with 0.05C activation two circle, then with 1C (～1mA/cm2) electric current Circulation 100 circle, investigates battery capacity decay.
2) negative pole low temperature analysis lithium test
First assemble graphite | | LiFePO4CR2032 button cell, step is with 1) in similar, the most again room temperature next Electric current density activation two circle of 0.1C, then discharges with 1C under the conditions of subzero 10 degree, investigates graphite surface analysis lithium degree.
3) graphite surface morphology observation
Li by electric discharge 15h | | graphite CR2032 battery is taken apart in glove box, clear by dimethyl carbonate (DMC) Wash graphite electrode surface, then its evacuation in glove box transfer chamber is processed so that it is the DMC on surface volatilizees completely.Then Transfer to SEM observes by electrode slice with special sealing container.The graphite that will discharge at low temperatures | | LiFePO4CR2032 button cell is taken apart in glove box, cleans graphite electrode surface by dimethyl carbonate (DMC), then will Its evacuation in glove box transfer chamber processes so that it is the DMC on surface volatilizees completely.Then with special sealing container by electrode Sheet is transferred to observe in SEM.
Embodiment 18
1) battery assembles and test
Assemble graphite | | LiCoO2Cycle performance of battery investigated by CR2032 button cell.Wherein positive electrode uses business Product LiCoO2.Active material in electrode fabrication, conductive agent, the ratio of binding agent is 84:8:8.Barrier film uses PE.Electrolyte is real Execute electrolyte in example 12.Negative pole is commercialization graphite, and in electrode fabrication, graphite is 92:8 with the ratio of binding agent.
Battery testing: graphite | | LiCoO2CR2032 button cell first with 0.05C activation two circle, then with 1C (～ 1mA/cm2) current cycle 100 encloses, and investigates battery capacity decay.
2) negative pole low temperature analysis lithium test
First assemble graphite | | LiCoO2CR2032 button cell, step is with 1) in similar, then the most at normal temperatures with Electric current density activation two circle of 0.05C, then discharges with 1C under the conditions of subzero 10 degree, investigates graphite surface analysis lithium degree.
Embodiment 19
1) electrolyte configuration
The first step, with LiTFSI as lithium salts, with 1,3 dioxolanes (DOL) and 1,2 dimethoxy-ethanes (DME) mix Liquid (volume ratio is 1:1) is that 1M LiTFSI/DOL+DME electrolyte prepared by solvent；Second step, precise 0.15g additive HO-CH2-CH2-(O-CH2-CH2)98-(O-CH(CH3)-CH2)67-(O-CH2-CH2)98-CH2-CH2-OH, is dissolved in 4.85g 1M In the electrolyte of LiTFSI/DOL+DME, obtain the electrolyte that additive mass fraction is 3%.Stand three days standby.More than walk Suddenly all complete in glove box (water oxygen content is respectively less than 0.1ppm).
2) battery assembles and test
Battery assembles: assemble Li-S battery, the impact that lithium metal surface pattern and battery capacity are decayed by additive.Its In the most extremely Graphene and the composite of sulfur, concrete manufacturing process is: first Graphene and high purity sulphur are ground by the mass ratio of 1:9 Mill uniformly, heats 15h the most again at 150 DEG C, presses after then adding conductive agent and binding agent mix homogeneously in the ratio of 7:2:1 Certain thickness is film forming in aluminum foil current collector.Electrolyte uses the present embodiment 1) in electrolyte add 2%LiNO3, barrier film is adopted With PE, negative pole uses lithium metal.
Battery testing: use Arbin BT2000 test system that battery is tested.First battery 0.1C is activated two Circle, then encloses by 0.5C current cycle 100.Investigation battery capacity decays.
Comparative example 1
Electrolyte configures
Precise 1.177g lithium hexafluoro phosphate (LiPF6) be dissolved in 8.823g Allyl carbonate (PC) and be configured to 1M LiPF6/ PC electrolyte, not doping.Stand three days standby.
Remaining step is similar to Example 1.
Comparative example 2
Electrolyte configures
1) first step, with LiPF6For lithium salts, mix liquid (volume with ethylene carbonate (EC) and diethyl carbonate (DEC) Ratio is 1:1) it is that 1M LiPF prepared by solvent6/ EC+DEC electrolyte, not doping.
2) battery assembles and test
Battery assembles: assemble Li | | graphite half-cell.Wherein graphite is commercialization graphite, in electrode fabrication graphite with The ratio of binding agent is 92:8, battery diaphragm use PE, electrolyte uses the 1 of this comparative example) in electrolyte.Assemble graphite ||LiFePO4Cycle performance of battery investigated by CR2032 button cell.Wherein positive electrode uses commodity LiFePO4.In electrode fabrication Active material, conductive agent, the ratio of binding agent is 8:1:1.Barrier film uses PE.Electrolyte is 1) in electrolyte.Negative pole is commodity Graphite, in electrode fabrication, graphite is 92:8 with the ratio of binding agent.
Battery testing: use Arbin BT2000 test system that battery is tested.Wherein Li | | graphite CR2032 button cell is with 0.1mA/cm2Discharge 15 hours, investigate cell voltage time graph, and graphite surface lithium metal sinks Long-pending pattern.graphite||LiFePO4CR2032 button cell is first with 0.05C activation two circle, then with 1C (～1mA/cm2) electric current Circulation 100 circle, investigates battery capacity decay.
3) negative pole low temperature analysis lithium test
First assemble graphite | | LiFePO4CR2032 button cell, step is with 1) in similar, the most at normal temperatures with Electric current density activation two circle of 0.05C, then discharges with 1C under the conditions of subzero 10 degree, investigates graphite surface analysis lithium degree.
4) graphite surface morphology observation
Li by electric discharge 15h | | graphite CR2032 battery is taken apart in glove box, clear by dimethyl carbonate (DMC) Wash graphite electrode surface, then its evacuation in glove box transfer chamber is processed so that it is the DMC on surface volatilizees completely.Then Transfer to SEM observes by electrode slice with special sealing container.The graphite that will discharge at low temperatures | | LiFePO4CR2032 button cell is taken apart in glove box, cleans graphite electrode surface by dimethyl carbonate (DMC), then will Its evacuation in glove box transfer chamber processes so that it is the DMC on surface volatilizees completely.Then with special sealing container by electrode Sheet is transferred to observe in SEM.
Comparative example 3
1) electrolyte configuration
The first step, with LiTFSI as lithium salts, with 1,3 dioxolanes (DOL) and 1,2 dimethoxy-ethanes (DME) mix Liquid (volume ratio is 1:1) is that solvent prepares 1M LiTFSI/DOL+DME electrolyte, not doping.
2) battery assembles and test
Battery assembles: assemble Li-S battery, the impact that lithium metal surface pattern and battery capacity are decayed by additive.Its In the most extremely Graphene and the composite of sulfur, concrete manufacturing process is: first Graphene and high purity sulphur are ground by the mass ratio of 1:9 Mill uniformly, heats 15h the most again at 150 DEG C, presses after then adding conductive agent and binding agent mix homogeneously in the ratio of 7:2:1 Certain thickness is film forming in aluminum foil current collector.Electrolyte uses 1) in electrolyte add 2%LiNO3, barrier film uses PE, negative pole Use lithium metal.
Battery testing: use Arbin BT2000 test system that battery is tested.First battery 0.1C is activated two Circle, then encloses by 0.5C current cycle 100.Investigation battery capacity decays.
Table 1 embodiment 1-15 and comparative example 1 septation pick up, barrier film and electrolyte contacts angle and barrier film electrical conductivity pair Ratio
Table 2 embodiment 1-10 and battery capacity attenuation verses in comparative example 1-3
Graphite in table 3 embodiment 17,18 and comparative example 2 | | LiFePO4CR2032 button cell cathode low temperature analysis lithium Degree contrasts
Embodiment Graphite surface analysis lithium degree
Embodiment 17 Without substantially analysis lithium phenomenon
Embodiment 18 Without substantially analysis lithium phenomenon
Comparative example 2 Analysis lithium phenomenon is serious
As it is shown in figure 1, comparative example 1 does not adds additive, embodiment 1,2,3 and 4 adds additive HO-CH2- CH2-(O-CH2-CH2)98-(O-CH(CH3)-CH2)67-(O-CH2-CH2)98-CH2-CH2-OH, it can be seen that in electrolysis Liquid adds between additive metacneme and electrolyte wellability be improved significantly, be in particular in carrying of barrier film pick up High.
As in figure 2 it is shown, in the case of in embodiment 1 with comparative example 1, other conditions are identical, in the electrolyte of embodiment 1 Addition additive metacneme is obviously reduced with the contact angle of electrolyte, illustrates that wellability is greatly improved；Barrier film and electricity Solve the infiltrating raising of liquid and can increase lithium ion transmission channel in barrier film, improve lithium ion stream and divide at the uniform of electrode surface Cloth degree, reduces the lithium ion stream risk in electrode surface Local enrichment, thus suppresses the growth of Li dendrite.
As it is shown on figure 3, after adding additive in the electrolyte of embodiment 1 and 2, being positioned at that curve uppermost is not Additivated 1M LiPF6/ PC, the curve being located below is followed successively by 1M LiPF6/ PC+ mass concentration is the additive of 0.2% With 1M LiPF6/ PC+ mass concentration is the curve of the additive of 0.5%；The activation polarization of copper surface lithium deposition has increased, Illustrate that additive can be attached to electrode surface, affect the lithium ion deposition site at electrode surface, thus dendrite inhibition generates；
As shown in Figure 4,5, not adding additive in comparative example 1, the most additivated lithium ion deposition morphology shows Typical dendritic crystalline, the most secondary barrier film of wearing of the deposition morphology of this shape causes internal short-circuit of battery；Embodiment 1 adds Additive, after adding additive, lithium ion is substantially greatly improved in the deposition morphology of copper foil surface, by comparative example 1 Sharp-pointed dendritic crystalline is changed into mossy, and surface particles becomes more mellow and fuller, greatly reduces its risk piercing through barrier film, Improve battery security；
As shown in Figure 6, curve located above is the battery capacity decay pattern of embodiment 1, and the curve being located below is right The battery capacity decay pattern of ratio 1, compares comparative example 1, and embodiment 1 adds Li after additive in the electrolytic solution | | LiFePO4Electricity The capability retention in pond has obtained the biggest lifting.By suppressing the formation in lithium metal surface of Li dendrite, except improving battery Safety outside also effectively reduce electrode surface area, reduce the extent of reaction between lithium metal and electrolyte, improve battery Cycle performance.
The foregoing is only the preferred embodiment of the invention, not in order to limit the invention, all at this Any amendment, equivalent and the improvement etc. made within the spirit of innovation and creation and principle, should be included in the invention Protection domain within.

Claims (9)

1. the additive of an electrolyte with dual Li dendrite inhibitory action, it is characterised in that the chemistry of described additive Formula is ABA or AB, wherein,
A is hydrophilic functional groups, selected from polyethylene glycol oxide HO-(CH2-CH2-O)n-H or polyhydric alcohol CnH2n+2-x(OH)xIn one, Wherein x >=3；
B is hydrophilic functional groups, the one in polypropylene oxide, alkyl phenol, straight-chain alkyl or branched hydrocarbyl.
The additive of a kind of electrolyte with dual Li dendrite inhibitory action is preparing electrolyte In application.
3. an electrolyte with dual Li dendrite inhibitory action, it is characterised in that include one as claimed in claim 1 There is the additive of the electrolyte of dual Li dendrite inhibitory action.
4. having a preparation method for the electrolyte of dual Li dendrite inhibitory action as claimed in claim 3, its feature exists In, including following preparation process:
1) weighing lithium salts and be dissolved in organic solvent, compound concentration is the solution of 1mol/L, and left at room temperature three days is standby；
2) described additive is dissolved in step 1) in the solution that obtains, i.e. obtain electrolyte, additive in described electrolyte Mass fraction be 0.05%～5%.
The preparation method of a kind of electrolyte with dual Li dendrite inhibitory action, its feature exists In, described lithium salts is the one in inorganic lithium salt or organic lithium salt.
The preparation method of a kind of electrolyte with dual Li dendrite inhibitory action, its feature exists In, described inorganic lithium salt is LiPF6、LiBF4、LiClO4、LiAsF6、LiNO3、LiI、LiCl、LiBr、LiCF3SO3Or LiC4F9SO3In one；Described organic lithium salt is LiN (CxF2x+1SO2)(CyF2y+1SO2)、LiC(SO2CF3)3、LiPFa (CF3)6-aOr LiPFb(C2F5)6-bIn one, wherein x, y, a, b are natural number, a, b≤6；Described organic solvent is carbonic acid third Alkene ester (PC), ethylene carbonate (EC), dimethyl carbonate (DMC), diethyl carbonate (DEC), Ethyl methyl carbonate (EMC), γ fourth Lactone (γ BL), oxolane (THF), 1,3 dioxolanes (DOL), dimethoxymethane (DMM), 1,2 dimethoxy-ethanes (DME) one or more mixed liquors or in tetraethyleneglycol dimethyl ether (TEGDME).
7. a battery with dual Li dendrite inhibitory action, it is characterised in that include a kind of tool as claimed in claim 3 Having the electrolyte of dual Li dendrite inhibitory action, also include battery case, anode, battery cathode and barrier film, described battery is born Pole is arranged on the negative pole district of described battery case, and described anode is arranged on the positive polar region of described battery case, described positive polar region and Negative pole district is provided with described electrolyte, and described positive polar region is separated by described barrier film with described negative pole district, then by described electricity Pond shell seals.
A kind of battery with dual Li dendrite inhibitory action, it is characterised in that described battery is just The material that pole is selected is cobalt acid lithium (LiCoO2), LiMn2O4 (LiMn2O4), lithium nickelate (LiNiO2), LiFePO4 (LiFePO4)、 CNT and sulfur composite, hollow carbon and sulfur composite, mesoporous carbon and sulfur composite, activated carbon and sulfur composite wood Material, graphite and sulfur composite, Graphene and the one in sulfur composite, metal-oxide, metal nitride or Carbon Materials Or several combination, the material that described battery cathode is selected is lithium metal or graphite electrode.
A kind of battery with dual Li dendrite inhibitory action, it is characterised in that described barrier film is adopted Be in polyethylene (PE), polypropylene (PP) or polyethylene-polypropylene-polyethylene composite diaphragm (PE-PP-PE) Kind.
CN201610649434.3A 2016-08-09 2016-08-09 A kind of additive with dual Li dendrite inhibitory action and application thereof Pending CN106252722A (en)

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