CN111566844A - Composite electrolyte - Google Patents
Composite electrolyte Download PDFInfo
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- CN111566844A CN111566844A CN201980008083.XA CN201980008083A CN111566844A CN 111566844 A CN111566844 A CN 111566844A CN 201980008083 A CN201980008083 A CN 201980008083A CN 111566844 A CN111566844 A CN 111566844A
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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
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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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
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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
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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
- 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
- H01M10/0568—Liquid materials characterised by the solutes
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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
- H01M10/0566—Liquid materials
- H01M10/0569—Liquid materials characterised by the solvents
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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
- H01M2300/0025—Organic electrolyte
- H01M2300/0028—Organic electrolyte characterised by the solvent
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The present invention provides a composite electrolyte comprising a nonwoven layer and a solid-liquid electrolyte provided on at least one surface of the nonwoven layer. The invention also relates to a battery containing the composite electrolyte.
Description
This application claims priority from european application EP 18305111.9 filed on 2/2018, the entire content of which is incorporated by reference into the present application for all purposes.
Technical Field
The present invention relates to a composite electrolyte comprising a solid-liquid electrolyte in the form of a gel for use in an electrochemical device, in particular a primary or secondary battery, a supercapacitor, an electrochromic display or a solar cell. The invention also relates to an electrochemical device comprising the composite electrolyte element and a method for the preparation thereof.
Background
Alkali metal batteries, in particular lithium ion batteries, are known. They are widely used for portable electronic devices, cameras, electric tools, electric vehicles, and the like.
Batteries comprising so-called "green sand" electrolytes are also known. "Green sand" electrolyte is defined as a composition comprising an inorganic oxide (e.g., Al) dispersed in a non-aqueous liquid electrolyte salt solution2O3、TiO2、SiO2) The solid-liquid composite electrolyte of (1). In certain versions of the volume fraction of the oxide, it is for the electrolyte system groupTypically, the liquid electrolyte is converted to a gel electrolyte. The use of "green sand" electrolytes greatly reduces the risk of electrolyte leakage that can occur with liquid electrolytes and enhances safety performance with their thermal stability and non-flammable inorganic characteristics.
Furthermore, the "green sand" electrolyte may exhibit higher ion transport and ionic conductivity than the starting liquid electrolyte, and also higher than the solid electrolyte.
EP 1505680 a2 discloses a battery comprising a non-aqueous electrolyte comprising an ion conducting salt, a non-aqueous anhydrous solvent and an oxide having an average particle size of less than 5 μm (such as SiO)2) The oxide is present in an amount of from 20 to 50 vol% (i.e., when the oxide is SiO)2When higher than 44% by weight) is present in the electrolyte.
International patent application PCT/EP 2017/071319 (published as WO 2018/041709 a1), filed 24.8.2017, discloses a battery comprising a solid-liquid electrolyte in the form of a gel, the electrolyte comprising at least one ion-conducting salt, at least one organic carbonate-based solvent, and precipitated silica. The addition of precipitated silica to the liquid electrolyte results in a stable gel over time without the roughening effects encountered when using other types of silica.
US 9722275 discloses a battery cell comprising (a) an anode; (b) a cathode structure; and (c) an ionically conductive protective layer on the surface of the anode and interposed between the anode and cathode structures. The protective layer has a porous membrane having pores therein and a "green sand" soft matter phase disposed in at least one of the pores, wherein the soft matter phase comprises oxide particles dispersed in a non-aqueous alkaline, basic, or transition metal salt solution. Thus, the "green sand" soft matter phase impregnates the porous membrane. The conductive protective layer may also act as a separator/electrolyte layer disposed between the anode and cathode structures. According to US 9722275, the material used as the porous film is not a critical factor in the preparation of the protective layer, and an example using a polyethylene-based microporous layer is provided.
Disclosure of Invention
It has been found that when a "green sand" solid-liquid electrolyte layer comprising precipitated silica is provided on at least one surface of the non-woven layer, a separator/electrolyte layer with increased stability can be obtained. The use of a nonwoven porous layer in combination with a solid-liquid electrolyte also provides a way to obtain an advantageous process for making a pouch battery, which comprises injecting the solid-liquid electrolyte into a preformed pouch comprising a nonwoven material.
Drawings
Fig. 1 shows a schematic view of a pouch battery cell of a single type and a stacked type.
Fig. 2 shows a schematic of a single pouch cell using a solid-liquid electrolyte and a non-woven layer.
Fig. 3 shows the cycle performance of the single cell units of example 1 and comparative example 1.
Fig. 4 shows the thermal exposure safety test of the stacked-type pouch battery cells of example 2 and comparative example 2
Detailed Description
A first object of the present invention is a composite electrolyte for an alkali metal battery, comprising:
-a nonwoven layer having a first and a second surface, and
-a solid-liquid electrolyte layer provided on at least one surface of the non-woven layer,
wherein the solid-liquid electrolyte layer comprises:
-at least one ion-conducting salt,
at least one organic carbonate-based solvent, and
-precipitated silica.
The expression "nonwoven" is used herein to refer to the usual fabric-like materials made of short and long fibers, bonded together by chemical, mechanical, thermal or solvent treatment. The nonwoven material is a porous material.
The nature of the fibers making up the nonwoven layer is not limited. Suitable nonwoven materials for the composite electrolyte of the present invention may be made of inorganic or organic fibers. Among the inorganic fibers, mention may be made of glass fibers. Among the organic fibers, mention may be made of cellulose or rayon fibers, carbon fibers, polyolefin fibers (such as polyethylene or polypropylene fibers), poly (paraphenylene terephthalamide) fibers, polyethylene terephthalate fibers, polyimide fibers or any other polymer that can be made in the form of fibers.
In the composite electrolyte of the present invention, a solid-liquid electrolyte layer is provided on at least one surface of the nonwoven layer. Preferably, a solid-liquid electrolyte layer is provided on each surface of the nonwoven layer.
The non-woven layer typically has a thickness comprised between 5 and 100 μm, preferably between 10 and 80 μm, more preferably between 10 and 50 μm.
Non-limiting examples of suitable nonwoven layers are those supplied under the trade name TF4035 by nippon kodoshi Corp (japan).
The one or two solid-liquid electrolyte layers typically have a thickness of no more than 100 μm. The one or more solid-liquid electrolyte layers may have a thickness of at least 5 μm, preferably at least 8 μm.
The composite electrolyte of the invention has a total thickness, which means the thickness of the non-woven layer and one or two solid-liquid electrolyte layers, which is generally greater than 10 μm, even greater than 15 μm. Preferably, the total thickness does not exceed 300 μm.
In an advantageous embodiment, the composite electrolyte of the invention has a thickness of from 25 to 120 μm. In a particularly advantageous embodiment, the composite electrolyte of the invention comprises a non-woven layer having a thickness of from 15 to 40 μm and solid-liquid electrolyte layers provided on each surface of the non-woven layer, each solid-liquid electrolyte layer having a thickness of from 8 to 35 μm.
The solid-liquid electrolyte layer comprises at least one ion conducting salt, at least one organic carbonate-based solvent, and precipitated silica.
Suitable ion-conducting salts are selected from the group consisting of:
(a)MeI，Me(PF6)，Me(BF4)，Me(ClO4) Me-bis (oxalato) borate ("MeBOB)”)，MeCF3SO3，Me[N(CF3SO2)2]，Me[N(C2F5SO2)2]，Me[N(CF3SO2)(RFSO2)]Wherein R isFIs C2F5、C4F9Or CF3OCF2CF2，Me(AsF6)，Me[C(CF3SO2)3]，Me2S, Me is Li or Na,
(b)
wherein R'FSelected from the group consisting of: F. CF (compact flash)3、CHF2、CH2F、C2HF4、C2H2F3、C2H3F2、C2F5、C3F7、C3H2F5、C3H4F3、C4F9、C4H2F7、C4H4F5、C5F11、C3F5OCF3、C2F4OCF3、C2H2F2OCF3And CF2OCF3And an
(c) Mixtures thereof.
When the solid-liquid electrolytes specifically referred to are those suitable for use in lithium ion batteries, the at least one ionically conductive salt is preferably selected from the group consisting of: LiPF6，LiBF4，LiClO4Lithium bis (oxalato) borate ("LiBOB"), LiN (SO)2F)2，LiN(CF3SO2)2，LiN(C2F5SO2)2，Li[N(CF3SO2)(RFSO2)]nWherein R isFIs C2F5、C4F9、CF3OCF2CF2，LiAsF6，LiC(CF3SO2)3And mixtures thereof. More preferably, the ion conducting salt is LiPF6。
The ion-conducting salt is preferably dissolved in the organic carbonate-based solvent at a concentration of between 0.5 and 5.0 moles, more preferably between 0.8 and 1.5 moles, still more preferably 1.0 moles.
Non-limiting examples of suitable organic carbonate-based solvents include unsaturated cyclic carbonates and acyclic carbonates.
Suitable unsaturated cyclic carbonates include cyclic alkylene carbonates such as Ethylene Carbonate (EC), Propylene Carbonate (PC), butylene carbonate, fluoroethylene carbonate and fluoropropylene carbonate. The preferred unsaturated cyclic carbonate is ethylene carbonate.
Suitable acyclic carbonates include dimethyl carbonate (DMC), diethyl carbonate (DEC), Ethyl Methyl Carbonate (EMC), and fluorinated acyclic carbonates such as those represented by the formula: r1-O-C(O)O-R2Wherein R is1And R2Independently selected from the group consisting of: CH (CH)3、CH2CH3、CH2CH2CH3、CH(CH3)2And CH2Rf, wherein Rf is C1 to C3 alkyl substituted with at least one fluorine atom, and further wherein R1Or R2At least one of which contains at least one fluorine atom.
Suitable solvents may additionally comprise an ester component selected from the group consisting of: propyl Propionate (PP), Ethyl Propionate (EP), and fluorinated acyclic carboxylic acid esters having the formula: r3-C(O)O-R4Wherein R is3Selected from the group consisting of: CH (CH)3、CH2CH3、CH2CH2CH3、CH(CH3)2、CF3、CF2H、CFH2、CF2R5、CFHR3And CH2Rf, and R4Independently selected from the group consisting of: CH (CH)3、CH2CH3、CH2CH2CH3、CH(CH3)2And CH2Rf, wherein R5Is C1 to C3 alkyl optionally substituted with at least one fluorine atom, and R3Is C1 to C3 alkyl substituted with at least one fluorine, and further wherein R3Or R4At least one of which contains at least one fluorine and when R is3Is CF2When H, R4Is not CH.
In a preferred embodiment, the at least one organic carbonate-based solvent is a mixture of at least one acyclic carbonate and at least one unsaturated cyclic carbonate. More preferably, the at least one organic carbonate-based solvent is a mixture of ethylene carbonate and ethyl methyl carbonate.
Preferably, the mixture of at least one acyclic carbonate and at least one unsaturated cyclic carbonate comprises at least one unsaturated cyclic carbonate and at least one acyclic carbonate in a ratio of from 1:4 to 1:1 by volume, more preferably from 1:2.5 to 1:1 by volume, still more preferably 1:1 by volume.
The solid-liquid electrolyte comprises precipitated silica. By "precipitated silica" is meant amorphous silica prepared by precipitation with an acidifying agent (e.g., sulfuric acid) from a solution containing a silicate (e.g., sodium silicate).
The precipitated silicas used in the present invention can be prepared by carrying out the processes described in EP 396450A, EP 520862A, EP 670813A, EP 670814A, EP 762992A, EP 762993A, EP 917519A, EP 1355856A, WO 03/016215, WO 2009/112458, WO 2011/117400, WO 2013/110659, WO 2013/139934, WO 2008/000761.
The precipitated silica used in the composite electrolyte of the present invention has a median particle size comprised in the range from 3.0 μm to 80.0 μm. The median particle size can be determined by laser diffraction using a MALVERN (MasterSizer 2000) particle sizer using Fraunhofer theory (Fraunhofer theory). The analytical protocol included a first complete deagglomeration of the precipitated silica sample to be performed prior to the laser diffraction measurement.
Complete deagglomeration of the precipitated silica samples was carried out directly in the sample dispersion unit of the MasterSizer 2000 by setting the following parameters until the median particle size change between two successive analyses was below 5%:
hydro 2000G sample Dispersion Unit
Stirring conditions: 500rpm
The pump conditions: 1250rpm
An ultrasonic probe: 100 percent
The measurement parameters:
masking range: 8 to 15 percent
Background measurement duration: 10s
The measurement duration: 10s
Delay between measurements: 1 s.
The time to reach a stable median particle size with this approach is typically about one hundred seconds.
In a preferred embodiment, the precipitated silica median particle size is in the range of from 3.0 to 80.0 μm, more preferably from 3.0 to 60.0 μm, still more preferably from 3.0 to 20.0 μm. In some embodiments, the median particle size may be greater than 5.0 μm, and even greater than 6.0 μm.
The precipitated silica is characterized by from 100 to 650m2BET specific surface area in g.
In a preferred embodiment of the invention, the precipitated silica has a particle size of from 100 to 280m2BET specific surface area in g. The precipitated silica typically has a particle size of at least 110m2A/g, in particular at least 120m2BET specific surface area in g. BET specific surface area is generally at most 270m2In particular up to 260m2/g。
In another preferred embodiment, the precipitated silica has a particle size of from 300 to 650m2BET specific surface area in g. The precipitated silica typically has a particle size of at least 310m2A/g, in particular at least 330m2BET specific surface area in g.
The BET specific surface area is determined according to The Brunauer-Emmett-Teller method described in The Journal of The American Chemical Society, Vol.60, p.309, 2.1938, and corresponds to The standard NF ISO 5794-1, appendix E (6.2010).
Suitable precipitated silicas may, for example, have:
from 100 to 270m2BET specific surface area/g, and median particle size of from 3.0 to 80.0. mu.m, or
From 300 to 650m2A BET specific surface area per gram, and a median particle size of from 3.0 to 80.0 μm.
Preferred precipitated silicas for use in the composite electrolytes of the present invention are characterized by having a bound water content of at least 2.5 wt.%, more preferably at least 4.0 wt.%.
Bound water content is determined from the difference between the loss on ignition at 1000 ℃ (measured according to DIN 55921, ISO 3262/11, ASTM D1208) and the loss of moisture measured at 105 ℃ (measured according to ISO 787/2, ASTM D280); this value is characteristic of the underlying structure of silicon dioxide.
The precipitated silica used in the present invention preferably exhibits a pH of between 6.3 and 8.0, more preferably between 6.3 and 7.6.
The pH was measured according to a modification of standard ISO 787/9 (pH of a 5% suspension in water) as follows: 5 grams of precipitated silica were weighed into a 200mL beaker in about 0.01 grams. 95mL of water (measured from a graduated cylinder) was then added to the precipitated silica powder. The suspension thus obtained was stirred vigorously (magnetic stirring) for 10 minutes. Then pH measurements were performed.
According to a particular embodiment, the precipitated silica used in the present invention has an aluminum content, calculated as aluminum metal, of greater than 0.25 wt.%, even greater than 0.30 wt.%, relative to the weight of the precipitated silica. The aluminium content may conveniently be up to 0.50 wt%.
Notable non-limiting examples of precipitated silicas that can be used in the present invention are, for example
43、
68B、
331 or
365, all commercially available from Solvay corporation.
The amount of precipitated silica present in the solid-liquid electrolyte is such that the electrolyte has the consistency of a gel. The term "gel" is intended to mean a semi-rigid colloidal dispersion of a solid and a liquid to produce a viscous, gelatinous product.
Preferably, the amount by weight of precipitated silica in the solid-liquid electrolyte is in the range of from 1.0% to 25.0%, preferably from 1.0% to 15.0%, relative to the total weight of the solid-liquid electrolyte.
According to a first embodiment of the invention, the solid-liquid electrolyte exhibits a sufficiently low viscosity, which makes it suitable for the production of pouch cells by injection. At 25 ℃ in 1s-1The viscosity may be in the range from 1.0 to 600pa.s at the shear rate of (a). At 25 ℃ in 1s-1The viscosity may conveniently be in the range from 1.5 to 600pa.s, from 2.0 to 600pa.s, even from 4.0 to 600pa.s, and also from 5.0 to 500pa.s, at the shear rate of (a).
In a first aspect of this first embodiment, the solid-liquid electrolyte comprises precipitated silica in an amount ranging from 1.0% to 8.5% by weight relative to the total weight of the electrolyte, the precipitated silica having from 100 to 270m2BET specific surface area in g. The amount by weight of precipitated silica may advantageously be from 2.0% to 8.0%, preferably from 3.0% to 8.0%, relative to the total weight of the electrolyte.
In a second aspect of this first embodiment, the solid-liquid electrolyte comprises precipitated silica in an amount ranging from 2.0% to 18.0% by weight relative to the total weight of the electrolyte, the precipitated silica having from 300 to 650m2BET specific surface area in g.
According to a second embodiment of the invention, the solid-liquid electrolyte is characterized by high mechanical properties, such that the solid-liquid electrolyte is inSpreading on the surface of the nonwoven porous layer may be conveniently carried out. At 25 ℃ in 1s-1The viscosity of the solid-liquid electrolyte of this second embodiment may conveniently be in the range from 600 to 10000pa.s at shear rates of. At 25 ℃ in 1s-1May even range from 600 to 5000pa.s, in some cases at 25 ℃ in 1s-1Even in the range from 600 to 2500 pa.s.
In a first aspect of this second embodiment, the solid-liquid electrolyte comprises precipitated silica in an amount ranging from 8.5 to 15.0%, even from 9.0 to 15.0% by weight relative to the total weight of the electrolyte, the precipitated silica having from 100 to 270m2BET specific surface area in g.
In a second aspect of this second embodiment, the solid-liquid electrolyte comprises precipitated silica in an amount ranging from 18 to 25.0%, even from 19.0 to 25.0% by weight relative to the total weight of the electrolyte, the precipitated silica having from 300 to 650m2BET specific surface area in g.
In an advantageous embodiment, the solid-liquid electrolyte comprises:
-at least one ion-conducting salt,
at least one organic carbonate-based solvent, and
-precipitated silica in an amount ranging from 1.0% to 8.5% by weight relative to the total weight of the electrolyte,
wherein the precipitated silica has a particle size of from 100 to 270m2A BET specific surface area per gram, and a median particle size of from 3.0 to 80.0 μm. In some cases, the median particle size may be greater than 5.0 μm, and even greater than 6.0 μm.
In a further preferred embodiment, the solid-liquid electrolyte comprises:
-at least one ion-conducting salt,
at least one organic carbonate-based solvent, and
-precipitated silica in an amount ranging from 8.5% to 15.0% by weight relative to the total weight of the electrolyte,
wherein the precipitated silica has a particle size of from 100 to 270m2A BET specific surface area per gram, and a median particle size of from 3.0 to 80.0 μm. In some cases, the median particle size may be greater than 5.0 μm, and even greater than 6.0 μm.
The solid-liquid electrolyte may also conveniently contain at least one additive selected from the group consisting of:
film-forming carbonates, such as Vinylene Carbonate (VC), Vinyl Ethylene Carbonate (VEC), fluoroethylene carbonate (FEC), difluoroethylene carbonate F2EC, allyl ethyl carbonate;
conductive coatings, such as polythiophene, poly (3, 4-ethylenedioxythiophene (PEDOT);
additional lithium salts, such as lithium bis (trifluorosulfonyl) imide, lithium oxalyldifluoroborate;
catalyst inhibitors, e.g. SO2、CS2A cycloalkyl sulfite;
solid Electrolyte Interphase (SEI) stabilizers, such as B2O3Organic borate esters, boroxines;
HF scavengers, such as tris (trimethylsilyl) borate (TMSB), tris (trimethylsilyl) phosphite (TMSP);
-gas production inhibitors such as 1, 3-Propane Sultone (PS), prop-1-ene-1, 3-sultone (PES);
surfactants, such as perfluoro-octyl-ethylene carbonate (PFO-EC);
passivating agents, such as hexafluoroisopropanol, succinic anhydride;
-an ionic liquid;
-a redox shuttle, and
-a flame retardant.
The composite electrolyte of the present invention may be manufactured by any method known in the art. The composite electrolyte may be prepared, for example, by the following method: wherein a solid-liquid electrolyte is applied to one or both surfaces of the nonwoven layer using coating means known to those skilled in the art.
In another object, the invention provides an electronic device, in particular a primary or secondary battery, a supercapacitor, an electrochromic display or a solar cell, comprising a composite electrolyte as defined above. All definitions and preferences defined above for the composite electrolyte and its components apply equally to the electronic device comprising the composite electrolyte.
The electronic device may be an alkali metal battery. The expression "alkali metal battery" is used herein to refer to lithium metal, lithium ion and sodium ion primary or secondary batteries.
The alkali metal battery may be of any type, such as cylindrical, button, prismatic, or in the form of a pouch.
The alkali metal battery comprises at least one positive electrode, at least one negative electrode and at least one composite electrolyte according to the invention arranged between the positive and negative electrodes. The composite electrolyte of the present invention provides not only spatial and electrical isolation between the negative electrode and the positive electrode, but also an electrolyte for ion transfer.
The composite electrolyte of the present invention is advantageously used to prepare pouch batteries.
Accordingly, an additional object of the present invention is a pouch battery comprising a composite electrolyte comprising a non-woven layer and a solid-liquid electrolyte provided on at least one surface of the non-woven porous layer.
In a first preferred embodiment, the solid-liquid electrolyte in the pouch cell comprises:
-at least one ion-conducting salt,
at least one organic carbonate-based solvent, and
-precipitated silica in an amount of from 1.0 to 8.5% by weight relative to the total weight of the electrolyte, the precipitated silica having from 100 to 270m2BET specific surface area in g.
In a second embodiment, the solid-liquid electrolyte in the pouch cell comprises:
-at least one ion-conducting salt,
at least one organic carbonate-based solvent, and
-withPrecipitated silica in an amount of from 2.0 to 17.0% by weight relative to the total weight of the electrolyte, the precipitated silica having from 300 to 650m2BET specific surface area in g.
The solid-liquid electrolytes defined above are characterized by a viscosity that makes them suitable for being directly injected into a preformed pouch comprising at least one positive electrode, at least one negative electrode and at least one non-woven porous layer located between the negative and positive electrodes to provide an efficient process for simultaneously preparing a composite electrolyte and a battery assembly. At 25 ℃ for 1s-1The viscosity of the solid-liquid electrolyte is generally in the range from 1 to 600pa.s, from 5 to 500pa.s at a shear rate of (a).
The invention therefore also relates to a method for producing an alkaline battery, preferably a lithium ion battery, comprising: providing an assembly comprising at least one positive electrode, at least one negative electrode and at least one non-woven layer between the negative electrode and the positive electrode, and injecting a solid-liquid electrolyte into the assembly such that a solid-liquid electrolyte layer is formed on at least one surface of the non-woven layer, and sealing the assembly. Preferably, a solid-liquid electrolyte layer is formed on each surface of the nonwoven layer.
The method may be applied to the manufacture of batteries comprising both one battery cell (single cell) and more than one battery cell (so-called "stack"). When applied to the manufacture of a battery comprising a battery cell stack, there are a suitable number of non-woven layers between each positive electrode and each negative electrode in the stack.
In a preferred aspect, the invention relates to a lithium or sodium ion battery (primary or secondary), preferably a lithium ion battery, more preferably a lithium ion secondary battery.
Suitable compounds for forming positive electrodes for lithium ion secondary batteries include, for example, compounds having the formula LiaAxByCzQ2(0.8<a<1.5, x + y + z ≦ 1, 0 ≦ x, y, z ≦ 1), wherein A, B, C is at least one metal selected from transition metals such as Co, Ni, Fe, Mn, Cr, and V, andq is a complexing element such as O or S. Preferred examples thereof may include LiCoO2、LiNi0.6Co0.2Mn0.2O2. Suitable compounds may be those having Li3-xM’yM”2-y(JO4)3Wherein 0. ltoreq. x.ltoreq.3, 0. ltoreq. y.ltoreq.2; m 'and M' are the same or different metals, at least one of them being a transition metal; JO4Preferably PO4It may be partially substituted with another oxyanion, wherein J is S, V, Si, Nb, Mo, or a combination thereof. Still more preferably, compound EA1 is of the formula Li (Fe)xMn1-x)PO4Wherein 0 ≦ x ≦ 1, wherein x is preferably 1 (i.e., having the formula LiFePO)4Lithium iron phosphate of (1).
Suitable compounds for forming a negative electrode for a lithium ion secondary battery preferably include:
graphitic carbon capable of intercalating lithium, typically in a form such as lithium-bearing powder, flakes, fibers, or spheres (e.g., mesocarbon microbeads);
-lithium metal;
lithium alloy compositions, notably including those described in US 6203944 and/or in WO 00/03444;
lithium titanates, generally of formula Li4Ti5O12To represent;
lithium-silicon alloys, commonly known as lithium silicide with a high Li/Si ratio, in particular of the formula Li4.4Lithium silicide of Si;
a lithium-germanium alloy comprising a compound having the formula Li4.4A crystalline phase of Ge.
The use of the composite electrolyte of the present invention significantly improves the safety of the battery by increasing the temperature at which the battery is subjected to significant catastrophic damage.
The invention will now be illustrated with reference to the following examples, which are intended to be illustrative only and are not intended to limit the scope of the invention.
If the disclosure of any patent, patent application, and publication incorporated by reference conflicts with the description of the present application to the extent that the terminology may become unclear, the description shall take precedence.
Examples of the invention
Raw materials
Precipitating silicon dioxide: from Soervi
331(T331) having a BET surface area SBET＝208m2(iv) g and a median particle size of 3.7 μm (measured by laser diffraction); bound water content 5.2%
A nonwoven layer: TF4035(TF4035) manufactured by japan high paper industry co., japan, contains rayon fibers and has a thickness of 35 μm and a porosity of about 40% to 80%.
Polyethylene layer: porous polyethylene layer manufactured by Kargard LLC
PE having a thickness of 25 μm and a porosity of about 40%
NCM 622: l from south Korea&LiNi manufactured by F Corp0.6Co0.2Mn0.2O2
BTR 918-2: natural graphite manufactured by Bifibrate Co (BTR)
SBR/CMC: styrene-butadiene rubber/carboxymethyl cellulose adhesive
General procedure for preparing electrolyte formulations
Liquid electrolyte: by using magnetic forcesThe mixer simply mixes to make the electrolyte. All components were added to one bottle and mixed until a clear solution was provided. First, lithium hexafluorophosphate (LiPF) was added6) Dissolved in a solvent. The solvent consisted of Ethylene Carbonate (EC) and Ethyl Methyl Carbonate (EMC) in a 3:7v/v ratio and then 2 wt% Vinylene Carbonate (VC). Then 0.5 wt% of 1, 3-Propane Sultone (PS) was added as an additive. This electrolyte was used as a reference electrolyte.
Solid-liquid electrolyte: all required components were added to one bottle and mixed by hand shaking until a gel was formed. The precipitated silica is dried and added to the liquid electrolyte in an inert atmosphere to avoid traces of water in the final product. By passing
M (Bemis) seals the bottle.
The compositions of these electrolytes are summarized in table 1.
TABLE 1
Using a Kinexus ultra + rheometer from Malvern (Malvern) (KNX 2310 with CP1/60SR2752 rotor) at 25 ℃ for 1s-1The viscosity of these electrolyte compositions was measured at shear rate.
Example 1 and comparative example 1
A solid-liquid electrolyte (electrolyte a in table 1) containing 10 wt% precipitated silica T331 was prepared as described in the general procedure.
A lithium-ion secondary battery (battery a according to the present invention) configured as shown in fig. 2 was prepared using the following procedure.
A natural graphite electrode having the following formulation was used as the negative electrode:
negative electrode formulation: BTR918-2+ Super-
+ SBR/CMC (by weight)Meter 97:1:1: 1); electrode loading: 6.8mg/cm2And 75-77 μm thick.
The electrolyte a is coated on the surface of the anode.
The non-woven layer TF4035 is placed on the layer formed by the electrolyte a.
A second layer of electrolyte a is coated on the exposed surface of the nonwoven layer.
A natural graphite electrode having the following formulation was used as the positive electrode:
the positive electrode formula: NCM622+ Super-
+8％
5130 (95: 3:2 by weight); electrode loading: 13.3mg/cm284-86 μm thick; theoretical capacity: 172 mAh/g.
The thickness of the composite electrolyte (non-woven + electrolyte a layer) was 60 ± 10 μm.
A single cell lithium ion battery having the same configuration as battery a but including a polyethylene layer instead of a nonwoven layer was prepared, including electrolyte a (comparative example 1). The thickness of the liquid electrolyte layer in the cell of reference 1 was about 100 μm.
The battery of example 1 (battery a) and the battery of comparative example 1 (reference 1) were subjected to a shaping step to form a Solid Electrolyte Interphase (SEI) between the electrolyte and the surface of the anode. They were charged at 25 ℃ for 3 hours at a C/10C rate.
C-rate is a measure of the rate at which the battery is charged or discharged. It is defined as the current divided by the theoretical current draw at which the battery will provide its nominal rated capacity in one hour.
The cells of example 1 and comparative example 1 were then subjected to a cycling test of charge/discharge cycling at C/2 rate. The results are shown in fig. 3.
The results show that the performance of the cell according to the invention (cell a) is better than that measured for the reference cell (reference 1) when after 100 charge/discharge cycles, thus indicating that the composite electrolyte with solid-liquid electrolyte and non-woven layer has better performance than the composite electrolyte using porous polyethylene layers.
Example 2 and comparative example 2
A solid-liquid electrolyte containing 4 wt% T331 (electrolyte C in table 1) was prepared as described in the general procedure.
An assembly for a pouch battery configured to contain a negative electrode, a positive electrode, and a nonwoven layer TF4035 disposed between the positive electrode and the negative electrode as shown in fig. 1 was prepared.
Negative electrode formulation: BTR918-2+ Super-
+ SBR/CMC (97: 1:1:1 by weight); electrode loading: 13.3mg/cm2。
The positive electrode formula: NCM622+ Super-
+8％
5130 (95: 3:2 by weight); electrode loading: 24.4mg/cm2Theoretical capacity: 172 mAh/g.
Electrolyte (C) was injected into the pouch cell using a syringe and sealed under vacuum.
A reference pouch cell lithium ion battery (reference 2) was prepared having the same electrode configuration but using a porous polyethylene layer instead of a nonwoven layer, and a reference liquid electrolyte as defined in table 1.
Cell C and reference 2 were subjected to a shaping step to form a solid electrolyte interphase between the electrolyte and the surface of the negative electrode. They were charged at 25 ℃ for 3 hours at a C/10C rate.
After formation, the cell was fully charged to 4.2V at C/5 to obtain a 100% state of charge.
Cell C and reference 2 were then subjected to a thermal exposure test under the following conditions: heating at 5 deg.C/min to 200 deg.C, and maintaining in explosion-proof chamber at 200 deg.C for 60 min.
The results of fig. 4 show that the cell according to the invention (cell C) has better performance than the reference cell (reference 2): compared with reference 2, the thermal stability of cell C was improved by 10min, 22 ℃.
Claims (15)
1. A composite electrolyte for an alkali metal battery comprising:
-a nonwoven layer having a first and a second surface, and
-a solid-liquid electrolyte layer provided on at least one surface of the non-woven layer, said solid-liquid electrolyte layer comprising at least one ion conducting salt, at least one organic carbonate based solvent and precipitated silica.
2. The composite electrolyte of claim 1, wherein solid-liquid electrolyte layers are provided on said first and second surfaces of the non-woven layer.
3. The composite electrolyte of claim 1 or 2, wherein the composite electrolyte has a thickness of from 10 to 300 μ ι η.
4. The composite electrolyte of any one of the preceding claims, wherein the precipitated silica is present in an amount of from 1.0 to 25.0% by weight relative to the total weight of the electrolyte.
5. The composite electrolyte of any one of the preceding claims, wherein the precipitated silica has a median particle size of from 3.0 to 80.0 μ ι η.
6. The composite electrolyte of any one of the preceding claims, wherein the precipitated silica has from 100 to 280m2BET specific surface area in g.
7. The composite electrolyte of any one of the preceding claims, whereinThe at least one ion conducting salt is selected from the group consisting of: LiPF6，LiBF4，LiClO4Lithium bis (oxalato) borate ("LiBOB"), LiN (CF)3SO2)2，LiN(C2F5SO2)2，Li[N(CF3SO2)(RFSO2)]nWherein R isFIs C2F5、C4F9、CF3OCF2CF2，LiAsF6，LiC(CF3SO2)3And mixtures thereof.
8. The composite electrolyte of any one of the preceding claims, wherein the at least one organic carbonate-based solvent is selected from the group consisting of: unsaturated cyclic carbonates, preferably selected from the group consisting of ethylene carbonate, propylene carbonate, butylene carbonate, fluoroethylene carbonate and fluoropropylene carbonate, and acyclic carbonates, preferably selected from the group consisting of dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, and fluorinated acyclic carbonates having the formula: r1-O-C(O)O-R2Wherein R is1And R2Independently selected from the group consisting of: CH (CH)3、CH2CH3、CH2CH2CH3、CH(CH3)2And CH2Rf, wherein Rf is C1 to C3 alkyl substituted with at least one fluorine atom, and further wherein R1Or R2At least one of which contains at least one fluorine atom.
9. A method for preparing the composite electrolyte of any one of claims 1-8, comprising coating the solid-liquid electrolyte on at least one surface of the nonwoven layer.
10. The method of claim 9, wherein the solid-liquid electrolyte has a temperature of 1s at 25 ℃-1A viscosity in the range from 600 to 10000pa.s measured at a shear rate of。
11. An electronic device comprising the composite electrolyte according to any one of claims 1 to 8.
12. The electronic device of claim 11, which is a battery.
13. The battery of claim 12, which is an alkaline battery, preferably a lithium ion battery.
14. A method for manufacturing a battery according to claim 12 or 13, comprising the steps of: providing an assembly comprising at least one positive electrode, at least one negative electrode and at least one non-woven layer between the negative electrode and the positive electrode, and injecting a solid-liquid electrolyte into the assembly such that a solid-liquid electrolyte layer is formed on at least one surface of the non-woven layer, and sealing the assembly.
15. The method of claim 14, wherein the solid-liquid electrolyte has a temperature of 1s at 25 ℃-1A viscosity in the range from 1.0 to 600pa.s measured at a shear rate of (a).
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP18305111.9 | 2018-02-02 | ||
| EP18305111 | 2018-02-02 | ||
| PCT/EP2019/052476 WO2019149873A1 (en) | 2018-02-02 | 2019-02-01 | Composite electrolyte |
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| CN111566844A true CN111566844A (en) | 2020-08-21 |
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ID=61198778
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| CN201980008083.XA Pending CN111566844A (en) | 2018-02-02 | 2019-02-01 | Composite electrolyte |
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| EP (1) | EP3747068A1 (en) |
| CN (1) | CN111566844A (en) |
| WO (1) | WO2019149873A1 (en) |
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| EP3747068A1 (en) | 2020-12-09 |
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