SE2250046A1 - Separator for a secondary cell - Google Patents

Separator for a secondary cell

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Publication number
SE2250046A1
SE2250046A1 SE2250046A SE2250046A SE2250046A1 SE 2250046 A1 SE2250046 A1 SE 2250046A1 SE 2250046 A SE2250046 A SE 2250046A SE 2250046 A SE2250046 A SE 2250046A SE 2250046 A1 SE2250046 A1 SE 2250046A1
Authority
SE
Sweden
Prior art keywords
separator
lithium
group
secondary cell
inorganic particles
Prior art date
Application number
SE2250046A
Inventor
Léo Duchêne
Original Assignee
Northvolt Ab
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Northvolt Ab filed Critical Northvolt Ab
Priority to SE2250046A priority Critical patent/SE2250046A1/en
Priority to PCT/EP2022/086048 priority patent/WO2023138846A1/en
Publication of SE2250046A1 publication Critical patent/SE2250046A1/en

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • 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
    • 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
    • H01M10/04—Construction or manufacture in general
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0567—Liquid materials characterised by the additives
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—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
    • 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
    • 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
    • H01M50/403—Manufacturing processes of separators, membranes or diaphragms
    • 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
    • H01M50/446—Composite material consisting of a mixture of organic and inorganic materials
    • 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
    • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
    • H01M50/451—Separators, membranes or diaphragms characterised by the material having a layered structure comprising layers of only organic material and layers containing inorganic material
    • 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
    • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • H01M50/491—Porosity
    • 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
    • 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
    • H01M2300/0034—Fluorinated solvents
    • 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

A porous separator for a secondary cell, the secondary cell comprising an anode, a cathode, and a liquid electrolyte, characterized in that the separator comprises inorganic particles attached to the separator, wherein the particles are functionalized; a method for its manufacture; a secondary cell comprising the separator; as well as a vehicle comprising such separator or secondary cell.

Description

SEPARATOR FOR A SECONDARY CELL FIELD OF THE INVENTION The present disclosure relates to a porous separator for a secondary cell. More particularly, the present disclosure relates to a porous separator for a secondary cell, where the separator comprises functionalized inorganic particles that are attached to the separator, a method for manufacturing the separator, as well as a vehicle comprising such separator or secondary cell.
TECHNICAL BACKGROUND Rechargeable batteries having high energy density and discharge voltage, in particular Li-ion batteries, are an important component in portable electronic devices and are a key enabler for the electrification of transport and large-scale storage of electricity. ln such batteries the cathode and anode are positioned close to each other and to avoid short-circuit that would cause battery failure and serious safety hazard due to overheating and potential fire, a separator is inserted between the cathode and anode to electrically isolate them from each other. The separator still allows ionic conductivity to permit charge and discharge of the battery. ln many common battery technologies, including Li-ion batteries, this ion transport occurs in a liquid electrolyte and the separator is typically a porous membrane that allows the electrolyte to contact both electrodes throughout its porous structure, while the sepa rator does not participate in the electrochemical reaction.
To reach higher energy densities, new types of batteries are being developed. ln rechargeable metal batteries, the anode consists of the metal whose corresponding cation carries the current in the electrolyte. ln these batteries, the cation is reduced to its metal form on the anode during charge instead of behind inserted into a host structure (e.g. graphite in Li-ion batteries). Removing such host material reduces the weight of the battery that can thus store a higher density of energy per mass and volume. However, rechargeable metal batteries, and in particular rechargeable lithium metal batteries (LMBs), face problems due to metal dendrite formation when the corresponding cation is deposited on the anode. That risk increases upon repetition of charging and discharging cycles or during particularly fast charging conditions. This is a disadvantage for the cycling stability as some of these dendrites can break off and get electronically disconnected, removing access to useful charge in the battery. lt also increases the risk for short-circuits in the secondary cell as dendrite can grow through the porous separator and contact the anode and cathode. lncreasing the uniformity of the metal plating is important to reduce the risk of dendrite formation. This uniformity is greatly influenced by the transport of corresponding metal ions in the electrolyte to the anode, as formalized in the so-called Sand's theory (Philos. Mag., 1901, 1, 45-79). The transference number of the specific metal ion, i.e. the share of the total current that is transported by said ions, is one of the parameters controlling the transport. A higher cation transference number is beneficial for smoother deposition of the metal and reduces the risk of dendrite formation (Energy Environ. Sci., 2016, 9, 3221-3229).
A recent study by Lee et al., (ACA Appl. |\/later. lnterfaces, 2020, 12, 37188-37196), shows that a dispersion of SiOZ-particles in a liquid electrolyte (so-called colloidal electrolyte) can improve the cation transference number. Surface groups naturally present on the SiOZ-particles interact with the anions in the electrolyte. As a result, more current is being supported by the cation, Li*, thereby increasing the lithium transference number.
However, dispersed particles in the electrolyte may come into contact and interact with both electrodes in an uncontrolled way and the stability of this dispersion over the battery lifetime is unknown. Implementing solutions to overcome these limitations can help to further improve the cation transference number and reduction of metal dendrite formation in electrochemical devices.
SUMMARY OF THE INVENTION An object ofthe present invention is to provide an improved separator for a secondary cell.
DETAILED DESCRIPTION OF THE INVENTION ln a first aspect, the present invention relates to a porous separator for a secondary cell, the secondary cell comprising an anode, a cathode, and a liquid electrolyte, characterized in that the separator comprises inorganic particles attached to the separator, wherein the particles are functionalized.
All aspects and embodiments disclosed herein can be combined with any other aspect and embodiment disclosed herein. ln one embodiment, the inorganic particles may be attached to one or two sides of the separator. Preferably, the inorganic particles may be attached to the side of the separator facing the cathode. Alternatively, the inorganic particles are attached to the side of the separator facing the anode. ln a further embodiment, the inorganic particles are dispersed throughout the separator. Preferably, the inorganic particles have an average size of from about 0.01 um to about 3 um, or from about 0.1 to about 1.0 um, 0.1 um to about 0.8 um, or from 0.1 um to about 0.15 um.
Controlling the surface chemistry of the inorganic particles enables optimization of the cation transference number. Attaching the functionalized inorganic particles to the separator avoids problems with sedimentation and uneven distribution of the particles in the liquid e|ectro|yte.
This improves the stability over time of the e|ectrochemica| device. ln one embodiment, the separator comprises a porous substrate comprising a po|ymer selected from the group consisting of PE, PP, PVDF, PVDF-HFP, PAN, PEI, Pl, ABS, PC or mixtures or copolymeric mixtures thereof. Preferably, the thickness of the porous substrate is in the range of from about 3 um to about 20 um. The separator preferably has a porosity in the range of from about 25% to about 75%, preferably from about 30% to about 50%. The term "porosity" as used herein denotes the percentage of void space in the separator material. ln a second aspect, the present invention relates to a secondary cell comprising an anode, a cathode, a liquid electrolyte, and the separator according to the first aspect of the invention positioned between the anode and the cathode. The inorganic particles may be attached to the side of the separator facing the cathode, or the inorganic particles may be attached to the side of the separator facing the anode, or the inorganic particles may be attached to the side of the separator facing the cathode as well as to the side facing the anode. Alternatively, the inorganic particles may be dispersed throughout the separator. ln one embodiment, the secondary cell is a lithium ion or lithium metal battery. ln one embodiment, the liquid electrolyte contains at least one lithium salt and at least one or more solvent selected from the group consisting of carbonate solvents and their fluorinated equivalents, diC1.4 ethers and their fluorinated equivalents and ionic liquids. The lithium salt is preferably one or more selected from the group consisting of lithium hexafluorophosphate (LiPF6), lithium bis(fluorosulfonyl)imide (LiFS|), lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), lithium (fluorosulfonyl) (trifluoromethanesulfonyl) imide (LEFTFSE), lithium bis(pentafluoroethanesulfonyl)imide (LiBETI), lithium (pentafluoroethanesulfonyl)(trifluoromethanesulfonyl)imide (LiPTFSI), lithium trifluoromethanesulfonate (LiOTf), lithium bis(oxalato)borate (LiBOB), lithium difluoro(oxalato)borate (LiDFOB), lithium difluorobis(oxalato)phosphate (LiDFOP), lithium tetrafluoro(oxalato)phosphate (LiTFOP), lithium tetrafluoroborate (LiBF4), lithium nitrate (LiNOg) lithium 2-trifluoromethyl-4,5-dicyanoimidazole (LiTDl). The solvent is preferably selected from the group consisting of 1,2-dimethoxyethane (DME), N-propyl-N-methylpyrrolidinium bis(fluorosulfonyl)imide (PYR13-FSI), N-propyl-N-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide (PYR13-TFSI), 1-butyl-1-methylpyrrolidinium bis(fluorosulfonyl)imide (PYR14-FSI), 1-butyl-1-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide (PYR14-TFSI), 1-ethyl-3-methylimidazolium bis(fluorosulfonyl)imide (E|\/|||\/I-FSI), 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide (E|\/|||\/I-TFSI), dimethyl carbonate (DMC), ethyl methyl carbonate (EMC), diethyl carbonate (DEC), ethylene carbonate (EC), and propylene carbonate (PC), and their fluorinated equivalents. The term "fluorinated equivalents" denotes that one or more of the hydrogen atoms are exchanged for fluorine atom(s). The liquid electrolyte may also contain functional additives in the form of salt or solvent additives, for example one or more additives selected from the group consisting of unsaturated cyclic carbonates, such as vinylene carbonate; fluorinated lithium phosphates; cyclic sulfates; and cyclic sulfones; as well as diluents, for example one or more diluents selected from the group consisting of fluorinated ethers, for example 1,1,2,2-tetrafluoroethyl 2,2,3,3-tetrafluoropropyl ether, or bis(2,2,2- trifluoroethyl)ether; fluorinated carbonates, for example or bis(2,2,2-trifluoroethyl) carbonate; fluorinated orthoformates, for example tris(2,2,2-trifluoroethyl) orthoformate; fluorinated phosphates, for example tris(2,2,2-trifluoroethyl) phosphate; fluorinated phosphites, for example tris(2,2,2-trifluoroethyl) phosphite; or fluorinated borates, for example tris(2,2,2- trifluoroethyl) borate. ln an embodiment, the positive electrode active material in the cathode is selected from one or more of a lithium transition metal composite oxide, including nickel (Ni), cobalt (Co) and manganese (|\/ln) as transition metals, preferably wherein the content of nickel is at least 83 mol% based on all transition metals; and a lithium metal phosphate, including at least one transition metal, preferably wherein the transition metal includes iron (Fe). ln an embodiment, the negative electrode active material in the anode is selected from one or more of a carbonaceous material, such as a graphitic material or a hard carbon or a combination thereof; silicon; silicon oxides described as SiOX, where O lithium metal; and lithium alloy. ln one embodiment each inorganic particle comprises or consists of a metal or metalloid selected from the group consisting of Si, Al, Mg, Zn, B, Zr, Ba, Ti, Pb, Li, Ta, and Nb, or a combination thereof. Preferably, each inorganic particle comprises a metal or metalloid selected from the group consisting of Si, Al, |\/lg, Zn, B, Zr, Ba, Ti, Pb, Li, Ta, and Nb, or a combination thereof. More preferably, the inorganic particles comprise a metal or metalloid, e.g. Si, Al, |\/lg, Zn, B, Zr, Ba, Ti, Pb, Li, Ta, and Nb, or a combination thereof, in the form of oxide, hydroxide, nitrite, nitride, sulphate, phosphate, or any combination thereof. Even more preferably, the inorganic particles are selected from the group consisting of SiOZ, AlzOg, ZrOZ, TiOZ, |\/|gO, ZnO, BaTiO4, BaTiO3, PbZrXTi1_XO3 (PZT) where x is any number between 1-10 (piezoelectric material),Ta2O_f,, NbzOg, AIO(OH) (boehmite), IV|g(OH)2, AI(OH)3, AlN, AI(NO3)3, BN, Si3N4, BaSO4, AIPO4, LiZO, LiZOZ, Li1_4Al0_4Ti1_6(PO4)3 (LATP), LiyLagZrzOlz (LLZO), LiAlOz. AlN is advantageous as it is a good heat conductor. An advantage with BaTiOg and PZT is that they have a high dielectric constant. ln one embodiment, the inorganic particles are all of the same kind. ln one embodiment of the present invention, the inorganic particles are functionalized with a monomolecular layer. The monomolecular layer constitutes molecular assemblies, where each molecule has the general formula X-Y-Z, wherein: X is a moiety, referred to as the head group, that is attached to the inorganic particle and is selected from the group consisting of PO(OR)2, wherein each R is independently selected from a hydrogen, a C1.100 alkyl, a C1.100 perhalogenated alkyl, preferably perfluorinated alkyl, a C6.100 aryl chain, a C6.100alkyl aryl chain, a C6.100 aryl alkyl chain; a P(O)O2IV| group or an OP(O)O2IV| group, wherein M is a metal cation, preferably one or several alkali metal cations, and more preferably one or several from the group comprising lithium, sodium, and potassium cations; an OPOgRz group, wherein each R is independently selected from a hydrogen, a C1.mo alkyl, a C1.mo perhalogenated alkyl, preferably perfluorinated alkyl, a Camo aryl chain, a Camoalkyl aryl chain, a Camo aryl alkyl chain; a sulphonic acid; a carboxylic acid; a thiol; and a silane, preferably a chlorosilane or an alkoxysilane; Y, referred to as the tail, is selected from a C1.mo alkyl; a C1.mo perhalogenated alkyl, preferably perfluorinated alkyl; a Camo aryl chain; a Camoalkyl aryl chain; a Camo aryl alkyl chain; (CH2(CH2),,O)n or (CH2(CH2),,S)n, where n is an integer between 1 and 50 and p is an integer between 1 and 50; and (CF(CF3)CF2O)m(CF2)2CF3, (CF2CF(CF3)O)m(CF2)2CF3, (CF2CF2CF2O)m(CF2)2CF3, or (CF2CF2O)m(CF2)CF3 where m is an integer between 1 and 100; wherein at least one hydrogen atom in all the above-mentioned non-perhalogenated chains may be substituted by a halogen atom, preferably fluorine; Z is a polar moiety, referred to as the terminal functional group, selected from the group consisting of OH, COOH, COH, C(S)OH, CONHZ, CSNHZ, NHZ, SH, CN, N02, PO(OH)2 and triazolium.
The X moiety preferably has a strong affinity to the surface of the inorganic particle. Preferably X is phosphonic acid, a P(O)O2M group, an OP(O)O2M group, or OPOgHz. ln a preferred embodiment the chain lengths for Y are Cago, Cm.ao, Cm.7o, or Cgogo, wherein some of the carbon atoms in the alkyl chain may be halogenated, such as by fluorine, or may be exchanged for an oxygen atom, or wherein the alkyl chain is perhalogenated, such as by fluorine atoms.
By attaching functionalized inorganic particles in, or to, the separator, according to the present invention, metal dendrite formation can be suppressed, and the cation transference number may be increased. The secondary cell according to the present invention may have a cation transference number of at least 0.4, 0.5, 0.6, 0.7, or 0.8.
Functionalizing the inorganic particle with a monolayer provides for a significant change in surface property even though the layer is very thin, such as a few nanometers. ln any of the embodiments disclosed herein, the inorganic particles are preferably functionalized with a self- assembled monolayer (SAM), i.e. the monomolecular layer may constitute SAM. A self- assembled monolayer is a one molecule thick layer that is spontaneously formed on the surface of the inorganic particle, i.e. the SAM may be formed on the inorganic particle without guidance from any external source. The person skilled in the art is well familiar with the concept of SAM.
The molecules forming the monolayer are organized in more or less ordered domains. SAM enables quick and low-cost fabrication, allows for a broad range and high control of functionalities, and provides for stability of the binding to the surface of the inorganic particle. Further, SAM can target specific substrates, which enables selective functionalization of the inorganic particles without affecting the rest of the separator materials. ln a third aspect, the present invention relates to a vehicle comprising a separator according to the first aspect, or a secondary cell according to the second aspect of the present invention. ln a fourth aspect, the present invention relates to a method for manufacturing a separator according to the first aspect of the present invention. ln one embodiment, the method comprises functionalizing the inorganic particle, followed by attaching the thereby functionalized inorganic particle to the separator. ln an alternative embodiment, the method comprises attaching the inorganic particle to the separator, followed by functionalizing the inorganic particle.

Claims (13)

Claims
1.A porous separator for a secondary cell, the secondary cell comprising an anode, a cathode, and a liquid electrolyte, characterized in that the separator comprises inorganic particles attached to the separator, wherein the particles are functionalized.
2.The separator according to claim 1, wherein the inorganic particles are attached to one or two sides of the separator.
3.The separator according to claim 1, wherein the inorganic particles are dispersed throughout the sepa rator.
4.The separator according to any one of the previous claims, wherein the inorganic particles have an average size of from about 0.01 um to about 3 um.
5.The separator according to claim 1, wherein the separator comprises a porous substrate comprising a polymer selected from the group consisting of PE, PP, PVDF, PVDF-HFP, PAN, PEI, Pl, ABS, PC or mixtures or copolymeric mixtures thereof.
6.The separator according to claim 5, wherein the thickness of the porous substrate is in the range of frorn about 3 um to about 2G um,
7.The separator according to claim 5 or 6, wherein the porous substrate has a porosity in the range of from about 25% to about 75%
8.The separator according to any one of the previous claims, wherein each inorganic particle comprises or consists of a metal or metalloid selected from the group consisting of Si, Al, Mg, Zn, B, Zr, Ba, Ti, Pb, Li, Ta, Nb.
9.The separator according to any one of the previous claims, wherein the inorganic particles comprise a metal or metalloid in the form of oxide, hydroxide, nitrite, nitride, sulphate, phosphate, or any combination thereof.
10.The separator according to any one of the previous claims, wherein the inorganic particles are selected from the group consisting of SiOZ, AlzOg, ZrOZ, TiOZ, |\/|gO, ZnO, BaTiO4, PbZrXTi1_XO3 where x is any number between 1-10 (piezoelectric material), Ta2O5, NbzOs, A|O(OH) (boehmite), IV|g(OH)2, AI(OH)3, AIN, Al(NO3)s, BN, Si3N4, BaSO4, AIPO4, Lizo, Lizoz, Li1_4A|0_4Ti1_6(Po4)3 (LATP), Lmagzrzolz (LLzo), LiAloz.
11.The separator according to any one of the previous claims, wherein the inorganic particles are all of the same kind.
12.The separator according to any one of the previous claims, wherein the inorganic particles are functionalized with a monomolecular layer.
13. The separator according to claim 12, wherein the monomolecular layer has the general formula X-Y-Z, wherein: X is a moiety that is attached to the inorganic particle and is selected from the group consisting of POlüRåg, wherein each R is independently selected from a hydrogen, a Cl. 100 alkyl, a C1.100 perhalogenated alkyl, preferably perfluorinated alkyl, a C6.100 aryl chain, a C6.100alkyl aryl chain, a C6.100 aryl alkyl chain; a P(O)O2IV| group or an OP(O)O2IV| group, wherein M is a metal cation, preferably one or several alkali metal cations, and more preferably one or several selected from the group comprising lithium, sodium, and potassium cations; an OPOgRz group, wherein each R is independently selected from a hydrogen, a C1.100 alkyl, a C1.100 perhalogenated alkyl, preferably perfluorinated alkyl, a C6.100 aryl chain, a C6.100alkyl aryl chain, a C6.100 aryl alkyl chain; a sulphonic acid; a carboxylic acid; a thiol; and a silane, preferably a chlorosilane or an alkoxysilane; Y is selected from a C1.100 alkyl; a C1.100 perhalogenated alkyl, preferably perfluorinated alkyl; a C6.100 aryl chain; a C6.100alkyl aryl chain; a C6.100 aryl alkyl chain; (CH2(CH2),,O)n or (CH2(CH2),,S)n, where n is an integer between 1 and 50 and p is an integer between 1 and 50; and (CF(CF3)CF2O)m(CF2)2CF3, (CF2CF(CF3)O)m(CF2)2CF3, (CF2CF2CF2O)m(CF2)2CF3, or (CF2CF2O)m(CF2)CF3, where m is an integer between 1 and 100; wherein at least one hydrogen atom in all the above-mentioned non-perhalogenated chains may be substituted by a halogen atom, preferably fluorine; Z is a polar moiety selected from the group consisting of OH, COOH, COH, C(S)OH, CONHZ, CSNHZ, NHZ, SH, CN, N02, PO(OH)2 and triazolium. A secondary cell comprising an anode, a cathode, a liquid electrolyte, and the separator according to any one of claims 1-13 positioned between the anode and the cathode. The secondary cell according to claim 14, wherein the inorganic particles are attached to the side of the separator facing the cathode. A secondary cell according to claim 14, wherein the inorganic particles are attached to the side of the separator facing the anode. A secondary cell according to claim 14, wherein the inorganic particles are attached to the side of the separator facing the cathode as well as to the side facing the anode. A secondary cell according to claim 14, wherein the inorganic particles are dispersed throughout the sepa rator. The secondary cell according to any one of claims 14-18, wherein the liquid electrolyte contains at least one lithium salt and at least one solvent selected from the group consisting of carbonate solvents and their fluorinated equivalents, diC1.4 ethers and their fluorinated equivalents and ionic liquids. The secondary cell according to claim 19, wherein the lithium salt is one or more salts selected from the group consisting of lithium hexafluorophosphate (LiPF6), lithium bis(fluorosulfonyl)imide (LiFSl), lithium bis(trifluoromethanesulfonyl)imide (LiTFSl), lithium (fluorosulfonyl) (trifluoromethanesulfonyl) imide (LiPTFSI), lithium bis(pentafluoroethanesulfonyl)imide (LiBETI), lithium (pentafluoroethanesulfonyl)(trifluoromethanesulfonyl)imide (LiPTFSI), lithium trifluoromethanesulfonate (LiOTf), lithium bis(oxalato)borate (LiBOB), lithium difluoro(oxalato)borate (LiDFOB), lithium difluorobis(oxalato)phosphate (LiDFOP), lithium tetrafluoro(oxalato)phosphate (LiTFOP), lithium tetrafluoroborate (LiBF4), lithium nitrate (LiNOg), lithium 2-trifluoromethyl-4,5-dicyanoimidazole (LiTD|); and the solvent is selected from the group consisting of 1,2-dimethoxyethane (DME), N-propyl-N- methylpyrrolidinium bis(fluorosulfonyl)imide (PYR13-FSI), N-propyl-N- methylpyrrolidinium bis(trifluoromethanesulfonyl)imide (PYR13-TFSI), l-butyl-l- methylpyrrolidinium bis(fluorosulfonyl)imide (PYR14-FSI), 1-butyl-1-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide (PYR14-TFSI), 1-ethyl-3-methylimidazolium bis(fluorosulfonyl)imide (E|\/|||\/I-FSI), 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide (E|\/|||\/I-TFSI), dimethyl carbonate (DMC), ethyl methyl carbonate (EMC), diethyl carbonate (DEC), ethylene carbonate (EC), and propylene carbonate (PC), and their fluorinated equivalents. The secondary cell according to claim 20, wherein the liquid electrolyte also contains one or more functional additives in the form of salts or solvent additives, for example one or more additives selected from the group consisting of unsaturated cyclic carbonates, such as vinylene carbonate; fluorinated lithium phosphates; cyclic sulfates; and cyclic sulfones; and diluents, for example one or more diluents selected from the group consisting of fluorinated ethers, for example 1,1,2,2-tetrafluoroethyl 2,2,3,3- tetrafluoropropyl ether, or bis(2,2,2-trifluoroethyl)ether; fluorinated carbonates, for example or bis(2,2,2-trifluoroethyl) carbonate; fluorinated orthoformates, for example tris(2,2,2-trifluoroethyl) orthoformate; fluorinated phosphates, for example tris(2,2,2- trifluoroethyl) phosphate; fluorinated phosphites, for example tris(2,2,2-trifluoroethyl) phosphite; or fluorinated borates, for example tris(2,2,2-trifluoroethyl) borate. The secondary cell according to any one of claims 14-21, wherein the cation transference number is at least 0.4, 0.5, 0.6, 0.7, or 0. Vehicle comprising a separator according to any one of claims 1-13 or a secondary cell according to any one of claims 14- A method for manufacturing the separator according to any one of claims 1-13, comprising a. Functionalizing the inorganic particle, followed by; b. Attaching the inorganic particle to the separator. A method for manufacturing the separator according to any one of claims 1-13, comprisinga. attaching the inorganic particle to the separator, followed by; b. functionalizing the inorganic particle. 12
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