CN110165295A - Composite electrolyte and the electrochemical appliance and electronic device for using it - Google Patents
Composite electrolyte and the electrochemical appliance and electronic device for using it Download PDFInfo
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- CN110165295A CN110165295A CN201910475646.8A CN201910475646A CN110165295A CN 110165295 A CN110165295 A CN 110165295A CN 201910475646 A CN201910475646 A CN 201910475646A CN 110165295 A CN110165295 A CN 110165295A
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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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- 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
- H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
- H01M10/0562—Solid materials
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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
- H01M10/056—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
- H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
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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
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0065—Solid electrolytes
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M2300/0017—Non-aqueous electrolytes
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- H01M2300/0082—Organic polymers
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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
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- H01M2300/0088—Composites
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Abstract
This application involves composite electrolyte and use its electrochemical appliance and electronic device.Specifically, the application provides a kind of composite electrolyte, and it includes: inorganic solid electrolyte；Organic solid-state electrolyte；Organic additive；And lithium salts, wherein the organic additive has the boiling point within the scope of 150 DEG C to 350 DEG C, and the total weight wherein based on the composite electrolyte, the content of the lithium salts is in the range of about 12wt% to about 50wt%.The composite electrolyte of the application has good conductivity.The lithium ion battery as made from the composite electrolyte of the application can realize the operation under room temperature and low temperature, and have low battery impedance and high battery capacity.
Description
Technical field
This application involves energy storage fields, and in particular to composite electrolyte and electrochemical appliance and electronic device using it.
Background technique
With the extensive use of the electronic equipments such as camera, DV, mobile phone and laptop, people couple
The performance requirement of electrochemical appliance (for example, lithium ion battery) is higher and higher.Lithium ion battery has energy density height, circulation longevity
The advantages that life length, memory-less effect, every field has been widely used in it.Electrolyte used in conventional lithium ion battery exists
Therefore inflammable hidden danger has become one of research direction as electrolyte substitute using the solid electrolyte of high security.It is single
One inorganic solid electrolyte conductivity with higher, but its intrinsic rigidity characteris leads to its patch between electrode plates
Close poor, interface impedance is larger, thus seriously hinders its application.Single organic solid-state electrolyte has centainly flexible
Property, it can be with electrode plates good fit, however its conductivity is lower (for example, the conductivity of PEO at room temperature is only 10-6S/
Cm), its practical application is thus hindered.Based on this, researcher increasingly focuses on Inorganic whisker solid electrolyte
Exploitation.The solid electrolyte of high security has become one of research direction.
In consideration of it, it is necessory to provide a kind of improved composite electrolyte and filled using its electrochemical appliance and electronics
It sets.
Summary of the invention
The embodiment of the present application by provide a kind of composite electrolyte and using its electrochemical appliance and electronic device with
At least one is at least solved in a way is present in the problems in related fields.
In one embodiment, this application provides a kind of composite electrolyte, it includes: inorganic solid electrolyte；It is organic
Solid electrolyte；Organic additive；And lithium salts, wherein the organic additive has within the scope of about 150 DEG C to about 300 DEG C
Boiling point, and the total weight wherein based on the composite electrolyte, the content of the lithium salts is in about 12wt% to about 50wt%
In the range of.
According to some embodiments of the present application, the organic additive includes below one or more: ethylene carbonate
(EC), propene carbonate (PC), sulfolane (SL), triethyl phosphate (TEP), succinonitrile (SN), n,N dimethylformamide
(DMF) and N, N dimethyl acetamide (DMAc).
According to some embodiments of the present application, based on the total weight of the composite electrolyte, the organic additive contains
Amount is in the range of about 3wt% to about 40wt%.
According to some embodiments of the present application, the inorganic solid electrolyte has with one of Types Below or a variety of
Structure: NASICON type, LISICON type, carbuncle type, (anti-) Ca-Ti ore type and sulfide type.
According to some embodiments of the present application, the inorganic solid electrolyte is selected from the following one or more:
Li1.3Al0.3Ti1.7(PO4)3(LATP)、Li1.5Al0.5Ge1.5(PO4)3(LAGP) and with formula Li7-yLa3-xAxZr2-yByO12Change
Object is closed, wherein 0≤x≤3,0≤y≤2, A is selected from Y, Nd, Sm or Gd, and B is selected from Nb or Ta.
According to some embodiments of the present application, based on the total weight of the composite electrolyte, the inorganic solid electrolyte
Content in the range of about 5wt% to about 50wt%.
According to some embodiments of the present application, the organic solid-state electrolyte is selected from the following one or more: polypropylene
Nitrile (PAN), polyethylene glycol oxide (PEO), polysiloxanes (PSO), polyvinylidene fluoride (PVDF), Kynoar-hexafluoropropene
(PVDF-HFP), polymethyl methacrylate (PMMA) and its derivative.
According to some embodiments of the present application, based on the total weight of the composite electrolyte, the organic solid-state electrolyte
Content in the range of about 10wt% to about 50wt%.
According to some embodiments of the present application, the composite electrolyte further includes porous matrix.
According to some embodiments of the present application, the porous matrix is selected from polyimides (PI), poly terephthalic acid second two
One of alcohol ester (PET), glass fibre and cellulose are a variety of.
According to some embodiments of the present application, the porosity of the porous matrix is in the range of about 20% to about 85%.
According to some embodiments of the present application, the composite electrolyte further includes the first additive, and described first adds
Add agent selected from the following one or more: 1,3,6- hexane trimethylsilyl nitrile (HTCN), ethylene glycol (double propionitrile) ether (EGBE), adiponitrile
(ADN), fluorinated ethylene carbonate (FEC), vinylene carbonate (VC), 1,3-propane sultone (PS), methane-disulfonic acid methylene
Ester (MMDS) and sulfuric acid vinyl ester (DTD).
According to some embodiments of the present application, based on the total weight of the composite electrolyte, first additive contains
Amount is in the range of about 0.1wt% to about 15wt%.
According to some embodiments of the present application, the composite electrolyte further includes Second addition, and described second adds
Add agent selected from the following one or more: alkyl phosphate, phosphorus nitrile compounds, fluorinated phosphate ester and fluoro-alkyl ether.
According to some embodiments of the present application, the alkyl phosphate is selected from the following one or more: trimethyl phosphate
(TMP), Trimethyl phosphite (TMPi), triphenyl phosphate (TPP), triphenyl phosphite (TPPi), tributyl phosphate (TBP) and
Tributyl phosphite (TBPi).
According to some embodiments of the present application, the phosphorus nitrile compounds are selected from the following one or more: hexa methoxy
Three phosphonitrile (PFPN) of ring phosphonitrile (HMPN), six ethoxy basic rings, three phosphonitrile (HETP) and five fluorine ethoxy basic rings.
According to some embodiments of the present application, the fluorinated phosphate ester is selected from the following one or more: three (2,2,2- tri-
Fluoro ethyl) phosphate (TFP), three (2,2,2- trifluoroethyl) phosphite esters (TTFP), two (2,2,2- trifluoroethyl) methyl phosphorus
Acid esters (BMP) and three (2,2,2- trifluoroethyl) diethylphosphates (TDP).
According to some embodiments of the present application, the fluoro-alkyl ether is selected from the following one or more: methyl perfluoro generation
Alkyl ether (MFE) and ethylperfluoro are for butyl ether (EFE).
According to some embodiments of the present application, based on the total weight of the composite electrolyte, the Second addition contains
Amount is in the range of about 0.1wt% to about 20wt%.
In another embodiment, the application provides a kind of electrochemical appliance, it includes: anode；Cathode；And the application
Composite electrolyte.
In another embodiment, the application provides a kind of electronic device, and it includes the electrochemical appliances of the application.
The additional level and advantage of the embodiment of the present application will be described partly in subsequent instruction, be shown or via this
Apply for the implementation of embodiment and illustrates.
Detailed description of the invention
Hereinafter will be briefly explained attached drawing necessary in order to describe the embodiment of the present application or the prior art in order to
Embodiments herein is described.It should be evident that the attached drawing in being described below is merely the section Example in the application.To this
For the technical staff of field, under the premise of not needing creative work, still can according to these attached drawings in illustrated by tie
Structure obtains the attached drawings of other embodiments.
Fig. 1 illustrates the surface microscopic topographic of the composite electrolyte of the application.
Fig. 2 illustrates cyclic curve of the lithium ion battery as made from embodiment 8 under the conditions of room temperature, 0.1C.
Fig. 3 illustrates cyclic curve of the lithium ion battery as made from embodiment 8 under the conditions of 4 DEG C, 0.1C.
Fig. 4 illustrates charging and discharging curve of the lithium ion battery as made from embodiment 2 under the conditions of 25 DEG C, 0.1C.
Fig. 5 illustrates the flammable test of the composite electrolyte piece of the application.
Specific embodiment
Embodiments herein will be shown hereinafter by detailed retouch.Embodiments herein is not construed as pair
The limitation of the application.
As used in this application, term " about " is to describe and illustrate small variation.Make when in conjunction with event or situation
Used time, the term can be referred to the example that wherein event or situation accurately occur and wherein event or situation pole approximatively occurs
Example.For example, when in conjunction with numerical value in use, term can be referred to ± 10% variation model less than or equal to the numerical value
Enclose, e.g., less than or equal to ± 5%, be less than or equal to ± 4%, be less than or equal to ± 3%, be less than or equal to ± 2%, be less than or
Equal to ± 1%, it is less than or equal to ± 0.5%, is less than or equal to ± 0.1% or is less than or equal to ± 0.05%.In addition, sometimes
In this application with range format presentation amount, ratio and other numerical value.It should be understood that such range format is for convenient and succinct
For the sake of, it and should neatly understand, not only comprising being expressly specified as the numerical value of scope limitation, but also include to be covered by the range
Interior all individual numbers or subrange, as explicitly specifying each numerical value and subrange.
It, can by the list of the project of term one of " or a variety of " connection in specific embodiment and claims
Mean any combination of listed item.For example, if listing project A and B, phrase " one of A and B or a variety of " meaning
Taste only A；Only B；Or A and B.In another example, if listing project A, B and C, phrase " one of A, B and C or
It is a variety of " mean only A；Or only B；Only C；A and B (excluding C)；A and C (excluding B)；B and C (excluding A)；Or the whole of A, B and C.
Project A may include discrete component or multiple element.Project B may include discrete component or multiple element.Project C may include single member
Part or multiple element.
One, composite electrolyte
Inorganic solid electrolyte and the simple composite of organic solid-state electrolyte can not be effectively improved the performance of electrolyte.Simply
It is compound usually effectively to improve the conductivity of Inorganic whisker solid electrolyte, and may cause organo-mineral complexing
Solid electrolyte can only use at high temperature, be unable to operate normally under room temperature or cryogenic conditions and simply just in organic nothing
Organic solvent is added in the compound solid electrolyte of machine will lead to that circulating battery stability is poor, this may improving conductivity then
It is that can aoxidize or restore in positive or negative pole because being not involved in the solvent of lithium ion dissociation, side reaction is caused to increase.
The application in organo-mineral complexing solid electrolyte by adding higher boiling organic additive and improving compound electric
The content of Xie Zhizhong lithium salts solves problem above.
Specifically, this application provides a kind of composite electrolyte, it includes: inorganic solid electrolyte；Organic solid-state electrolysis
Matter；Higher boiling organic additive；And high-content lithium salts.In some embodiments, the composite electrolyte further includes more
Hole matrix.In some embodiments, the composite electrolyte further includes additional additive.
Inorganic solid electrolyte
In some embodiments, the inorganic solid electrolyte is lithium ion conductor.
In some embodiments, the inorganic solid electrolyte has with one of Types Below or a variety of structures:
NASICON type, LISICON type, carbuncle type, (anti-) Ca-Ti ore type and sulfide type.
In some embodiments, the inorganic solid electrolyte has NASICON type or carbuncle type.NASICON type or
Conductivity with higher (is greater than 10 to the inorganic solid electrolyte of carbuncle type at room temperature-4S/cm), and have good
Stability and the stability to electrode plates in thermal stability, air.
In some embodiments, the inorganic solid electrolyte is selected from the following one or more: Li1.3Al0.3Ti1.7
(PO4)3(LATP)、Li1.5Al0.5Ge1.5(PO4)3(LAGP) and with formula Li7-yLa3-xAxZr2-yByO12Compound, wherein 0≤
X≤3,0≤y≤2, A is selected from Y, Nd, Sm or Gd, and B is selected from Nb or Ta.
In some embodiments, the inorganic solid electrolyte has one of zero dimension, one-dimensional, 2 and 3 dimensional organization
Or it is a variety of.
In some embodiments, the inorganic solid electrolyte is one of entity structure and porous structure or a variety of.
In some embodiments, the total weight based on the composite electrolyte, the content of the inorganic solid electrolyte exist
In the range of about 5wt% to about 50wt%.By the total weight of the composite electrolyte, when the content of inorganic solid electrolyte exists
When within the scope of this, the mechanical strength of composite electrolyte is preferable, can inhibit Li dendrite puncture；And film forming is preferable, is not easy to be torn.
In some embodiments, the total weight based on the composite electrolyte, the content of the inorganic solid electrolyte exist
In the range of about 10wt% to about 40wt%.In some embodiments, the total weight based on the composite electrolyte, it is described inorganic
The content of solid electrolyte is in the range of about 15wt% to about 30wt%.
Organic solid-state electrolyte
In some embodiments, the organic solid-state electrolyte is selected from the following one or more: polyacrylonitrile (PAN),
Polyethylene glycol oxide (PEO), polysiloxanes (PSO), polyvinylidene fluoride (PVDF), Kynoar-hexafluoropropene (PVDF-
HFP), polymethyl methacrylate (PMMA) and its derivative.
In some embodiments, the content of the total weight based on the composite electrolyte, the organic solid-state electrolyte exists
In the range of about 10wt% to about 50wt%.By the total weight of the composite electrolyte, when the organic solid-state electrolyte
When content is less than about 10wt%, organic solid-state electrolyte does not have the effect of support film forming；When the organic solid-state electrolyte
When content is greater than about 50wt%, the conductivity of organic solid-state electrolyte is deteriorated, and is unfavorable for battery and runs at room temperature.
In some embodiments, the content of the total weight based on the composite electrolyte, the organic solid-state electrolyte exists
In the range of about 15wt% to about 30wt%.In some embodiments, the total weight based on the composite electrolyte, it is described organic
The content of solid electrolyte is in the range of about 15wt% to about 25wt%.
Higher boiling organic additive
Organic additive in the composite electrolyte of the application has the boiling point within the scope of about 150 DEG C to about 350 DEG C.
In some embodiments, the organic additive includes below one or more: ethylene carbonate (EC), carbonic acid
Acrylic ester (PC), sulfolane (SL), triethyl phosphate (TEP), succinonitrile (SN), n,N dimethylformamide (DMF) and N, N bis-
Methylacetamide (DMAc).
In some embodiments, the total weight based on the composite electrolyte, the content of the organic additive is about
In the range of 3wt% to about 40wt%.In some embodiments, the total weight based on the composite electrolyte, it is described organic to add
Add the content of agent in the range of about 10wt% to about 40wt%.In some embodiments, based on the total of the composite electrolyte
Weight, the content of the organic additive is in the range of about 20wt% to about 30wt%.
Inorganic solid electrolyte, organic solid-state electrolyte in the composite electrolyte of the application, higher boiling organic additive
Collective effect improves the conductivity of lithium ion, improves the interfacial wettability between electrolyte and electrode plates, enhances compound
The toughness of electrolyte and the stickiness between pole piece reduce battery impedance, enable to transport under battery room temperature and cryogenic conditions
Row, improves battery capacity.
High-content lithium salts
In the composite electrolyte of the application, based on the total weight of the composite electrolyte, the content of the lithium salts is about
In the range of 12wt% to about 50wt%.In some embodiments, the total weight based on the composite electrolyte, the lithium salts
Content is in the range of about 20wt% to about 45wt%.In some embodiments, the total weight based on the composite electrolyte, institute
The content of lithium salts is stated in the range of about 28wt% to about 45wt%.
In some embodiments, the lithium salts is selected from the following one or more: double fluorine sulfimide lithiums (LiFSI), six
Lithium fluophosphate (LiPF6), lithium perchlorate (LiClO4), di-oxalate lithium borate (LiBOB), difluorine oxalic acid boracic acid lithium (LiDFOB), three
Fluorine methanesulfonic acid lithium (CF3SO3) and bis trifluoromethyl sulfimide lithium (LiTFSI) Li.
Inorganic solid electrolyte in the composite electrolyte of the application,Organic solid-state electrolyte、Higher boiling organic additive WithHigh-content lithium salts collective effect stablizes combined electrolysis confrontation lithium metal, and the pair between composite electrolyte and pole piece is effectively reduced
Reaction improves the cyclical stability of the lithium ion battery using the composite electrolyte.
Porous matrix
The mechanical strength and flexibility of composite electrolyte can be improved in porous matrix, and is conducive to composite electrolyte and electrode
Fitting between pole piece.
In some embodiments, the porous matrix is selected from polyimides (PI), polyethylene terephthalate
(PET), one of glass fibre and cellulose or a variety of.
In some embodiments, the porosity of the porous matrix is in the range of about 20% to about 85%.In some realities
It applies in example, the porosity of the porous matrix is in the range of about 30% to about 50%.
Other additives
In some embodiments, the composite electrolyte further includes the first additive, and first additive is selected from
It is below one or more: 1,3,6- hexane trimethylsilyl nitrile (HTCN), ethylene glycol (double propionitrile) ether (EGBE), adiponitrile (ADN), fluorine
For ethylene carbonate (FEC), vinylene carbonate (VC), 1,3-propane sultone (PS), methane-disulfonic acid methylene ester (MMDS)
With sulfuric acid vinyl ester (DTD).Inorganic solid electrolyte, organic solid-state electrolyte, higher boiling organic additive add with described first
Add agent that can play the role of protecting pole piece, improves the capacity of battery.
In some embodiments, the total weight based on the composite electrolyte, the content of first additive is about
In the range of 0.1wt% to about 15wt%.In some embodiments, the total weight based on the composite electrolyte, described first
The content of additive is in the range of about 0.5wt% to about 10wt%.In some embodiments, based on the composite electrolyte
Total weight, the content of first additive is in the range of about 1wt% to about 5wt%.
In some embodiments, the composite electrolyte further includes Second addition, and the Second addition is selected from
It is below one or more: alkyl phosphate, phosphorus nitrile compounds, fluorinated phosphate ester and fluoro-alkyl ether.Second addition
Agent can play fire retardation.
In some embodiments, the alkyl phosphate is selected from the following one or more: trimethyl phosphate (TMP), Asia
Trimethyl phosphate (TMPi), triphenyl phosphate (TPP), triphenyl phosphite (TPPi), tributyl phosphate (TBP) and phosphorous acid three
Butyl ester (TBPi).
In some embodiments, the phosphorus nitrile compounds are selected from the following one or more: hexakis-methoxy basic ring phosphonitrile
(HMPN), three phosphonitrile (PFPN) of six ethoxy basic rings, three phosphonitrile (HETP) and five fluorine ethoxy basic rings.
In some embodiments, the fluorinated phosphate ester is selected from the following one or more: three (2,2,2- trifluoroethyls)
Phosphate (TFP), three (2,2,2- trifluoroethyl) phosphite esters (TTFP), two (2,2,2- trifluoroethyl) methyl phosphorodithioates
(BMP) and three (2,2,2- trifluoroethyl) diethylphosphates (TDP).
In some embodiments, the fluoro-alkyl ether is selected from the following one or more: methyl perfluoro substituted alkyl ether
(MFE) and ethylperfluoro is for butyl ether (EFE).
In some embodiments, the total weight based on the composite electrolyte, the content of the Second addition is about
In the range of 0.1wt% to about 20wt%.In some embodiments, the total weight based on the composite electrolyte, described second
The content of additive is in the range of 0.5wt% to about 10wt%.In some embodiments, based on the total of the composite electrolyte
Weight, the content of the Second addition is in the range of 1wt% to about 5wt%.
The composite electrolyte of the application is in quasi- solid-state form (as shown in Figure 1)." quasi- solid union electrolyte " refers to solid-state
A certain amount of liquid electrolyte is accommodated in electrolyte, wherein liquid electrolyte is filled in the solid electrolyte knot as decentralized medium
In structure, so that composite electrolyte is apparently in solid-state.The mechanical strength and mechanical property of quasi-solid electrolyte are between liquid and solid-state
Between electrolyte, electrical conduction mechanism is identical as liquid electrolyte, therefore has good chemical property.
Two, electrochemical appliance
The electrochemical appliance of the application includes any device that electrochemical reaction occurs, its specific example includes all kinds
One-shot battery, secondary cell, fuel cell, solar battery or the capacitor of class.Particularly, which is that lithium is secondary
Battery, including lithium metal secondary cell, lithium ion secondary battery, lighium polymer secondary battery or the secondary electricity of lithium ion polymer
Pond.In some embodiments, the electrochemical appliance of the application includes the composite electrolyte of anode, cathode and the application.
Cathode
The material of cathode used in the electrochemical appliance of the application is that can occlude to electrochemistry, release lithium ion etc.
The substance of metal ion.
In some embodiments, cathode includes lithium metal.
In some embodiments, cathode includes lithium metal layer and netted insulating layer, wherein the setting of netted insulating layer is in lithium gold
It include hole on netted insulating layer, the aperture in the hole is about 10nm to about 500nm, and porosity is at least one surface belonged to
About 10%- about 50%, the insulating layer with a thickness of about 500 μm of about 50nm-.Insulating layer material can be selected from styrene-fourth two
Alkene rubber (SBR), nylon, polyacrylic acid (PAA), polyvinyl alcohol (PVA), poly- acetic acid (PLA), gathers carboxymethyl cellulose (CMC)
Vinyl-vinyl acetate copolymer, PEVA/PLA, polymethacrylates (PMMA)/tetrahydro perfluoro capryl acrylate
(TAN), polyethylene oxide (PEO), polymethacrylates (PMMA), polyamide (PA), polycaprolactone (PCL), poly- ethyl acyl
Imines (PEI), polycaprolactam, polyethylene (PE), polyethylene terephthalate (PET), polyolefin, polyphenylene oxide (PPE),
Polyvinyl chloride (PVC), polyvinylidene chloride (PVDC), polyvinylidene fluoride (PVDF), poly- (vinylidene fluoride-co- hexafluoro third
Alkene) (PVDF-HFP), polyvinylpyridine, polylactic acid (PLA), polypropylene (PP), polybutene (PB), poly terephthalic acid fourth two
Alcohol ester (PBT), polyamide (PA), polyimides (PI), polycarbonate (PC), polytetrafluoroethylene (PTFE) (PTFE), polystyrene (PS),
Polyester (PE), acrylonitrile-butadiene-styrene (ABS) (ABS), poly- (methyl methacrylate) (PMMA), polyformaldehyde (POM), polysulfones
(PES), styrene-acrylonitrile (SAN), polyacrylonitrile (PAN), ethane-acetic acid ethyenyl ester (EVA), phenylethylene-maleic anhydride
(SMA), at least one of vinyl (Vinyl).Lithium metal layer with a thickness of about 1 μm-about 500 μm.
In some embodiments, cathode includes lithium metal layer and passivation layer, and lithium metal surface is arranged in the passivation layer
In at least part, the passivation layer includes particle shape passivation layer and membranaceous passivation layer, the passivation layer with a thickness of about
100nm- about 600nm, when passivation layer is particle shape, partial size is about 10nm- about 500nm.In some embodiments, cathode includes
The layer of carbonaceous material of lithium metal layer and setting on the metal layer.In some embodiments between lithium metal layer and layer of carbonaceous material also
It can further include polymeric layer.Layer of carbonaceous material is selected from artificial graphite, natural graphite, graphene, carbon nanotube, in carbon fiber
At least one.
Anode
It can include any public in the prior art with material positive in the case of this application, composition and its manufacturing method
The technology opened.In some embodiments, the anode recorded in just extremely U.S. Patent application US9812739B, to be cited in full text
Mode be incorporated herein.
In some embodiments, anode includes collector and the anode active material layer on the collector.Anode is living
Property material include reversibly be embedded in and deintercalate lithium ions at least one lithiumation intercalation compound.In some embodiments, positive
Active material includes composite oxides.In some embodiments, which contains lithium and selects from cobalt, manganese and nickel
At least one element.
In some embodiments, positive electrode active materials include, but are not limited to:
LiaA1-bXbD2(0.90≤a≤1.8,0≤b≤0.5),
LiaE1-bXbO2-cDc(0.90≤a≤1.8,0≤b≤0.5,0≤c≤0.05),
LiaE2-bXbD4(0.90≤a≤1.8,0≤b≤0.5),
LiaE2-bXbO4-cDc (0.90≤a≤1.8,0≤b≤0.5,0≤c≤0.05),
LiaNi1-b-cCobXcDα(0.90≤a≤1.8,0≤b≤0.5,0≤c≤0.05,0 α≤2 <),
LiaNi1-b-cCobXcO2-αTα(0.90≤a≤1.8,0≤b≤0.5,0≤c≤0.05,0 < α < 2),
LiaNi1-b-cCobXcO2-αT2(0.90≤a≤1.8,0≤b≤0.5,0≤c≤0.05,0 < α < 2),
LiaNi1-b-cMnbXcDα(0.90≤a≤1.8,0≤b≤0.5,0≤c≤0.05,0 α≤2 <),
LiaNi1-b-cMnbXcO2-αTα(0.90≤a≤1.8,0≤b≤0.5,0≤c≤0.05,0 < α < 2),
LiaNi1-b-cMnbXcO2-αT2(0.90≤a≤1.8,0≤b≤0.5,0≤c≤0.05,0 < α < 2),
LiaNibEcGdO2(0.90≤a≤1.8,0≤b≤0.9,0≤c≤0.5,0.001≤d≤0.1),
LiaNibCocMndGeO2(0.90≤a≤1.8,0≤b≤0.9,0≤c≤0.5,0≤d≤0.5,0.001≤e≤
0.1)、
LiaNiGbO2(0.90≤a≤1.8,0.001≤b≤0.1),
LiaCoGbO2(0.90≤a≤1.8,0.001≤b≤0.1),
LiaMnGbO2(0.90≤a≤1.8,0.001≤b≤0.1),
LiaMn2GbO4(0.90≤a≤1.8,0.001≤b≤0.1),
QO2、QS2、LiQS2、V2O5、LiV2O5、LiIO2、LiNiVO4、Li(3-f)J2(PO4)3(0≤f≤2)、Li(3-f)Fe2
(PO4)3(0≤f≤2) or LiFePO4,
Wherein, A is selected from Ni, Co, Mn and their any combination；X selected from Al, Ni, Co, Mn, Cr, Fe, Mg, Sr,
V, rare earth element and their any combination；D is selected from O, F, S, P and their any combination；E is selected from Co, Mn and they
Any combination；T is selected from F, S, P and their any combination；G is selected from Al, Cr, Mn, Fe, Mg, La, Ce, Sr, V and it
Any combination；Q is selected from Ti, Mo, Mn and their any combination；I is selected from Cr, V, Fe, Sc, Y and theirs is any
Combination；And J is selected from by V, Cr, Mn, Co, Ni, Cu and their any combination.
In some embodiments, positive electrode active materials are selected from cobalt acid lithium (LiCoO2), lithium nickel cobalt manganese (NCM) ternary material,
LiFePO 4 (LiFePO4), LiMn2O4 (LiMn2O4) or their any combination.
In some embodiments, positive electrode active materials can have a coating on the surface thereof, or can with coating
Another compound mixing.The coating may include from the oxide of coating element, the hydroxide for coating element, coating element
Oxyhydroxide, coat the carbonic acid oxonium salt of element and coat at least one coating element selected in the hydroxyl carbonate of element
Compound.Compound for coating can be amorphous or crystallization.
In some embodiments, the coating element contained in the coating may include Mg, Al, Co, K, Na, Ca, Si, Ti,
V, Sn, Ge, Ga, B, As, Zr or their any combination.Coating can be applied by any method, as long as this method is not right
The performance of positive electrode active materials has an adverse effect.For example, this method may include to any coating well known in the art
Method, such as spraying, impregnating.
Anode active material layer further includes adhesive, and optionally includes conductive material.Adhesive improves positive-active
The combination of material granule to each other, and also improve the combination of positive electrode active materials and collector.
In some embodiments, adhesive includes, but are not limited to: polyvinyl alcohol, hydroxypropyl cellulose, diacetyl fiber
Element, polyvinyl chloride, the polyvinyl chloride of carboxylation, polyvinyl fluoride, the polymer of the oxygen containing ethylidene, polyvinylpyrrolidone, polyurethane,
Butadiene-styrene rubber, the ring that polytetrafluoroethylene (PTFE), polyvinylidene fluoride, polyethylene, polypropylene, butadiene-styrene rubber, acrylic acid (ester) are changed
Oxygen resin, nylon etc..
In some embodiments, conductive material includes, but are not limited to: the material based on carbon, the material based on metal, conduction
The mixture of polymer and they.In some embodiments, the material based on carbon is selected from natural graphite, artificial graphite, carbon black, second
Acetylene black, Ketjen black, carbon fiber or any combination thereof.In some embodiments, it is fine to be selected from metal powder, metal for the material based on metal
Dimension, copper, nickel, aluminium, silver.In some embodiments, conducting polymer is polyphenylene derivatives.
In some embodiments, collector can be aluminium, but not limited to this.
Anode can be prepared by preparation method well known in the art.For example, anode can obtain by the following method:
Active material, conductive material and adhesive are mixed in solvent, to prepare active material composite, and combined the active material
Object coats on a current collector.In some embodiments, solvent may include N-Methyl pyrrolidone etc., but not limited to this.
Three, electronic device
The purposes of the electrochemical appliance of the application is not particularly limited, and can be used for any electronics well known in the prior art
Device.In one embodiment, the electrochemical appliance of the application can be used for, but be not limited to, the imported calculating of laptop, pen
Machine, removable computer, e-book player, portable phone, portable facsimile printer, portable copier, portable printer, head
Wear formula stereophone, video recorder, LCD TV, Portable cleaning machine, portable CD player, Mini Disk, transceiver, electronic recording
Sheet, calculator, storage card, portable recorder, radio, backup power source, motor, automobile, motorcycle, moped, from
Driving, luminaire, toy, game machine, clock and watch, electric tool, flash lamp, camera, home-use large-scale battery and lithium from
Sub-capacitor etc..
Illustrate the preparation of lithium ion battery by taking lithium ion battery as an example and in conjunction with specific embodiments below, this field
The skilled person will understand that preparation method described in this application is only example, other any suitable preparation methods are in this Shen
Please in the range of.
Embodiment
Illustrate below the composite electrolyte according to the embodiment of the present application and comparative example and lithium ion battery as made from it into
Row Performance Evaluation.
One, the preparation (button cell) of lithium ion battery
1, the preparation of cathode
Using lithium metal or lithium alloy as cathode.
2, positive preparation
By positive electrode active materials (LiFePO4Or cobalt acid lithium (LCO)), conductive black and polyvinylidene fluoride (PVDF) according to
80%: 10%: 10% mass ratio mixing, is added N-Methyl pyrrolidone (NMP) and is used as solvent, stir evenly, obtain solid
Content is the anode sizing agent of 0.75wt%.Anode sizing agent obtained is coated on plus plate current-collecting body aluminium foil, is dried at 110 DEG C
It is dry, obtain anode.In obtained anode, the coating weight of positive electrode active materials is about 6g/cm2To about 7g/cm2。
3, the preparation of composite electrolyte
Organic polymer is dissolved in corresponding solvent and (be see the table below), the organic addition of higher boiling is added until completely dissolved
Agent, lithium salts and inorganic solid electrolyte.Mixed slurry is coated, is dried (for using acetone, acetonitrile or tetrahydro furan
It mutters the composite electrolyte of (THF) as solvent, it is 60 minutes dry at 60 DEG C；It is molten for being used as using dimethyl carbonate (DMC)
The composite electrolyte of agent is dried in vacuo 10 hours at 60 DEG C).
| Organic polymer | Solvent |
| PVDF | DMC (dissolves) at 80 DEG C |
| PVDF-HFP | Acetone or DMC (being dissolved at 80 DEG C) |
| PSO | THF |
| PEO | Acetonitrile |
4, the preparation of lithium ion battery
Anode, composite electrolyte and cathode are sequentially assembled, lithium ion button shape cell is obtained.
Two, test method
1, the test method of the lithium ion conductivity of composite electrolyte
Composite electrolyte is clipped between stainless steel substrates, stainless steel substrates are connected to by electrochemical operation by battery clip
It stands.Electrolyte impedance is measured using electrochemical alternate impedance spectrum.Be calculate by the following formula the lithium of the conductivity of composite electrolyte from
Electron conductivity:
σ=L/RS
Wherein, L is the thickness of composite electrolyte, and R is the impedance that measurement obtains, S is stainless steel substrates and composite electrolyte
Contact area.
2, the charge-discharge test method of lithium ion battery
Lithium ion battery obtained is subjected to charge-discharge performance test under the conditions of room temperature or 4 DEG C, obtains lithium ion battery
Charging and discharging curve and for the first time with 20 times electric discharge after capacity.For with LiFePO4For the lithium ion battery of positive electrode active materials,
Charging/discharging voltage range is 2.75-3.8V.For using LCO as the lithium ion battery of positive electrode active materials, charging/discharging voltage range
For 3-4.35V.Specific discharge capacity is calculated with the electricity that every gram of active material is released.
3, the cycle performance test method of lithium ion battery
Lithium ion battery obtained is subjected to cycle performance test under the conditions of room temperature or 4 DEG C, lithium ion battery is obtained and follows
Ring performance curve and for the first time with 20 times electric discharge after capacity.For with LiFePO4For the lithium ion battery of positive electrode active materials,
Charging/discharging voltage range is 2.75-3.8V.For using LCO as the lithium ion battery of positive electrode active materials, charging/discharging voltage range
For 3-4.35V.Specific discharge capacity is calculated with the electricity that every gram of active material is released.
4, the flammable test method of lithium ion battery
Solid electrolyte is placed in culture dish, with the lighter or match catalytic combustion lighted.Then, fire source is moved
It opens, whether observation solid electrolyte burns away, and observes the variation of the color of solid electrolyte, form and dimension.If removing
After fire source, electrolyte does not burn away and then shows that solid electrolyte has well without the variation of color, form and dimension
Safety.
Three, test result
Table 1 illustrates the composite electrolyte (comparative example 1-3) without organic additive and the compound electric containing organic additive
Solve the composition and conductivity at room temperature of matter (embodiment 1-21).The result shows that composite electrolyte exists after addition organic additive
Conductivity at room temperature is significantly improved.For example, (that is, embodiment after adding organic additive SL on the basis of comparative example 3
16), the conductivity of composite electrolyte at room temperature increases about 546%.
According to comparative example 4 and the circulation of embodiment 2 as a result, the stabilization that the lithium salts of low concentration is unfavorable for lithium ion battery is followed
Ring.(about 12wt% can effectively improve the cycle performance of lithium ion battery to about 50wt%) lithium salts to high-content.
Using each comparative example shown in table 1 and embodiment composite electrolyte and use LiFePO4As positive-active material
Expect that lithium ion battery is made.It discharges after testing the battery impedance and first circle and 20 circles of obtained lithium ion battery at room temperature
Specific capacity, the results are shown in Table 2.The result shows that the lithium ion battery as made from the composite electrolyte without organic additive exists
It is unable to run at room temperature.Organic additive is added in composite electrolyte can significantly reduce the resistance of obtained lithium ion battery
It is anti-, and realize the stable operation of lithium ion battery at room temperature.Fig. 4 illustrates the lithium ion battery as made from embodiment 2 and exists
25 DEG C, the charging and discharging curve under the conditions of 0.1C.
Table 2
Embodiment 24,25 and 26 is similar to embodiment 9,21 and 22 respectively, the difference is that only that embodiment 24-26 makes
Use LCO as positive electrode active materials, and (3-4.35V) is tested under high voltage charge status.Its lithium ion battery
Specific discharge capacity after battery impedance and first circle and 20 circles, the results are shown in Table 3.The above result shows that the compound electric of the application
It solves matter and is suitable for high-voltage lithium ion batteries.In addition, according to embodiment 24,25 and 26 in table 3, the presence of additional additive is helped
In the high voltage stability for improving composite electrolyte.
Table 3
Embodiment 27 is similar to Example 8, but it is 70%, with a thickness of 16 microns of polyimide foraminous that it, which contains porosity,
Matrix.Embodiment 28 joined 2%VC on the basis of embodiment 27.Embodiment 29 joined on the basis of embodiment 28
5%TMP.Lithium ion battery made from composite electrolyte as the application is subjected to flammable test (as shown in Figure 5).As a result table
Bright, the lithium ion battery as made from the composite electrolyte of the application does not occur combustion phenomena, has high security.
Table 4 illustrates the performance of embodiment 27-29.
Table 4
Using the composite electrolyte of embodiment 8 shown in table 1 and use LiFePO4As positive electrode active materials be made lithium from
Sub- battery.The first circle specific discharge capacity of obtained lithium ion battery is tested at room temperature and 4 DEG C.As shown in table 5, the application
Composite electrolyte not only realizes operation at room temperature, but also realizes the operation under low temperature.Fig. 2 and 3 is respectively shown by reality
Apply cyclic curve of the lithium ion battery made from example 8 under the conditions of room temperature and 4 DEG C.The above result shows that the combined electrolysis of the application
Matter ensure that the performance of lithium ion battery under cryogenic, greatly extend the application range of lithium ion battery.
Table 5
In the whole instruction to " embodiment ", " section Example ", " one embodiment ", " another citing ", " citing ",
The reference of " concrete example " or " some examples ", representated by mean at least one embodiment or citing in this application
Contain special characteristic, structure, material or characteristic described in the embodiment or citing.Therefore, throughout the specification
The description that each place occurs, such as: " in some embodiments ", " in embodiment ", " in one embodiment ", " another
In a citing ", " in a citing ", " in particular examples " or " citing " are not necessarily identical in reference the application
Embodiment or example.In addition, special characteristic herein, structure, material or characteristic can be in any suitable manner one
It is combined in a or multiple embodiments or citing.
Although having demonstrated and having described illustrative embodiments, those skilled in the art should understand that above-described embodiment cannot
It is interpreted the limitation to the application, and can be in the case where not departing from spirit herein, principle and range to implementation
Example is changed, alternatives and modifications.
Claims (12)
1. a kind of composite electrolyte, it includes:
Inorganic solid electrolyte；
Organic solid-state electrolyte；
Organic additive；And
Lithium salts,
Wherein the organic additive has the boiling point within the scope of 150 DEG C to 350 DEG C, and
Total weight wherein based on the composite electrolyte, the content of the lithium salts is in the range of 12wt% to 50wt%.
2. composite electrolyte according to claim 1, wherein the organic additive includes below one or more: carbon
Vinyl acetate, propene carbonate, sulfolane, triethyl phosphate, succinonitrile, N, N-dimethylformamide and N, N dimethyl acetyl
Amine.
3. composite electrolyte according to claim 1, wherein the inorganic solid electrolyte has with one in Types Below
Kind or a variety of structures: NASICON type, LISICON type, carbuncle type, (anti-) Ca-Ti ore type and sulfide type.
4. composite electrolyte according to claim 1, wherein the inorganic solid electrolyte is selected from the following a kind of or more
Kind: Li1.3Al0.3Ti1.7(PO4)3、Li1.5Al0.5Ge1.5(PO4)3With with formula Li7-yLa3-xAxZr2-yByO12Compound, wherein
0≤x≤3,0≤y≤2, A is selected from Y, Nd, Sm or Gd, and B is selected from Nb or Ta.
5. composite electrolyte according to claim 1, wherein the total weight based on the composite electrolyte, described inorganic solid
The content of state electrolyte in the range of 5wt% to 50wt%, the content of the organic solid-state electrolyte 10wt% extremely
In the range of 50wt%, and the content of the organic additive is in the range of 3wt% to 40wt%.
6. composite electrolyte according to claim 1, wherein the organic solid-state electrolyte is selected from the following a kind of or more
Kind: polyacrylonitrile, polyethylene glycol oxide, polysiloxanes, polyvinylidene fluoride, Kynoar-hexafluoropropene, polymethylacrylic acid
Methyl esters and its derivative.
7. composite electrolyte according to claim 1, wherein the composite electrolyte further includes porous matrix, wherein
The porous matrix is selected from one of polyimides, polyethylene terephthalate, glass fibre and cellulose or a variety of,
And wherein the porosity of the porous matrix is in the range of 20% to 85%.
8. composite electrolyte according to claim 1, wherein the composite electrolyte further includes the first additive, institute
It is selected from the following one or more to state the first additive: 1,3,6- hexane trimethylsilyl nitrile, ethylene glycol (double propionitrile) ether, adiponitrile, fluorine
For ethylene carbonate, vinylene carbonate, 1,3- propane sultone, methane-disulfonic acid methylene ester and sulfuric acid vinyl ester.
9. composite electrolyte according to claim 1, wherein the composite electrolyte further includes Second addition, institute
It is selected from the following one or more to state Second addition: alkyl phosphate, phosphazene compound, fluorinated phosphate ester and fluoro-alkyl
Ether.
10. composite electrolyte according to claim 9, in which:
The alkyl phosphate is selected from the following one or more: trimethyl phosphate, Trimethyl phosphite, triphenyl phosphate, Asia
Triphenyl phosphate, tributyl phosphate and tributyl phosphite；
The phosphazene compound is selected from the following one or more: hexakis-methoxy basic ring phosphonitrile, six ethoxy basic rings, three phosphonitrile and five fluorine
Three phosphonitrile of ethoxy basic ring；
The fluorinated phosphate ester is selected from the following one or more: three (2,2,2- trifluoroethyl) phosphates, three (2,2,2- trifluoros
Ethyl) phosphite ester, two (2,2,2- trifluoroethyl) methyl phosphorodithioates and three (2,2,2- trifluoroethyl) diethylphosphates；With
And
The fluoro-alkyl ether is selected from the following one or more: methyl perfluoro substituted alkyl ether and ethylperfluoro are for butyl ether.
11. a kind of electrochemical appliance, it includes:
Anode；
Cathode；And
Composite electrolyte described in any claim in -10 according to claim 1.
12. a kind of electronic device, it includes the electrochemical appliances described in claim 11.
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