WO2014048505A1

WO2014048505A1 - Lithium- ion battery

Info

Publication number: WO2014048505A1
Application number: PCT/EP2012/069298
Authority: WO
Inventors: Serhii KRASAVTSEV
Original assignee: Entonik Holding Ag; LITTAU, Galina
Priority date: 2012-09-28
Filing date: 2012-09-28
Publication date: 2014-04-03

Abstract

The present invention relates to a novel anode composition, novel electrolyte, and lithium ion batteries comprising these.

Description

Lithium Ion Battery

Background of the Invention

The present invention relates to rechargeable Lithium-Ion-Polymer Cells for use in the whole field of secondary batteries. There is an increasing demand for batteries which are high in energy per mass and volume and in addition high in power. In the field of Lithium-Ion-Batteries the use of polymer electrolytes has become more and more important, which also attracts wide attention in research for improvements.

There are several advantages of using polymer electrolyte in a Lithium-Ion-Battery: free of leakage of electrolyte, low vapour pressure, high flexibility in size and shape and low self discharge rates, even at higher temperatures. The main draw backs are still high internal resistance and poor cycle life. The first can be compensated by increasing the electrode areas which results in poor energy per volume and weight. The second is still related to the poor basic chemistry which results in the build up of passivating layers on the negative and the positive electrode. During the formation there is a cleavage of C-H Bonds of the organic solvent, which forms hydrogen and reduces capacity. In addition with increasing passivating layer with time and higher temperatures the inner resistance increases too, resulting in decreasing power capability. The novel anode composition and/or novel electrolyte provide one or more of these advantages.

Summary of the Invention

The present invention relates in a first aspect to an anode composition for use in a lithium ion battery comprising a heteroaromatic salt and a lithium ion intercalating compound.

In a second aspect the present invention relates to an electrolyte for use in a lithium ion battery comprising an electrolytic salt and a non-aqueous solvent, wherein the electrolytic salt is a heteroaromatic salt.

In a third aspect the present invention relates to an electrolyte for use in a lithium ion battery comprising a separator compound and a non-aqueous solvent, wherein the separator compound is a polysaccharide ester.

In a fourth aspect the present invention relates to a lithium ion battery comprising:

(a) an anode comprising an anode composition according to the present invention, (b) a electrolyte; and

(c) a cathode.

In a fifth aspect the present invention relates to a lithium ion battery comprising

(a) an anode comprising an anode composition according to the present invention;

(b) a electrolyte; and

(c) a cathode comprising a cathode composition,

wherein the cathode is producible by a process comprising the steps:

(i) providing a mixture of a transition metal and a lithium salt in a solution of a solvent and an organic polymer;

(ii) applying the mixture to an cathode current collector; and

(iii) evaporating the solvent.

In a sixth aspect the present invention relates to a lithium ion battery comprising

(a) an anode,

(b) a electrolyte according to the present invention; and

(c) a cathode comprising a cathode composition,

wherein the cathode is producible by a process comprising the steps:

(ii) applying the mixture to an cathode current collector; and

(iii) evaporating the solvent.

In a seventh aspect the present invention relates to a lithium ion battery comprising

(a) an anode;

(b) a electrolyte according to the present invention; and

(c) a cathode.

Detailed Description of the Invention

Before the present invention is described in detail below, it is to be understood that this invention is not limited to the particular methodology, protocols and reagents described herein as these may vary. It is also to be understood that the terminology used herein is for the purpose of describing particular embodiments only, and is not intended to limit the scope of the present invention which will be limited only by the appended claims. Unless defined otherwise, all technical and scientific terms used herein have the same meanings as commonly understood by one of ordinary skill in the art. Throughout this specification and the claims which follow, unless the context requires otherwise, the word "comprise", and variations such as "comprises" and "comprising", will be understood to imply the inclusion of a stated integer or step or group of integers or steps but not the exclusion of any other integer or step or group of integers or steps. In the following passages different aspects of the invention are defined in more detail. Each aspect so defined may be combined with any other aspect or aspects unless clearly indicated to the contrary. In particular, any feature indicated as being preferred or advantageous may be combined with any other feature or features indicated as being preferred or advantageous.

Several documents are cited throughout the text of this specification. Each of the documents cited herein (including all patents, patent applications, scientific publications, manufacturer's specifications, instructions, etc.), whether supra or infra, are hereby incorporated by reference in their entirety. Nothing herein is to be construed as an admission that the invention is not entitled to antedate such disclosure by virtue of prior invention.

In the following definitions of the terms: "alkyl", "cycloalkyl", "alicyclic system", "aryl", "heteroaryl", "heteroaralkyl", "alkenyl", "cycloalkenyl", "alkynyl" and "optionally substituted" are provided. These terms will in each instance of its use in the remainder of the specification have the respectively defined meaning and preferred meanings.

The term "alkyl" refers to a saturated straight or branched carbon chain. Preferably, the chain comprises from 1 to 10 carbon atoms, i.e. 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10 e.g. methyl, ethyl methyl, ethyl, propyl, z^'so-propyl, butyl, z^'so-butyl, tert-butyl, pentyl or hexyl, heptyl, or octyl. Alkyl groups are optionally substituted.

The term "alicyclic system" refers to mono, bicyclic, tricyclic or polycyclic version of a cycloalkyl or heterocycloalkyl comprising at least one double and/or triple bond. However, an alicyclic system is not aromatic or hetero aromatic, i.e. does not have a system of conjugated double bonds/free electron pairs. Thus, the number of double and/or triple bonds maximally allowed in an alicyclic system is determined by the number of ring atoms, e.g. in a ring system with up to 5 ring atoms an alicyclic system comprises up to one double bond, in a ring system with 6 ring atoms the alicyclic system comprises up to two double bonds. Thus, the "cycloalkenyl" as defined below is a preferred embodiment of an alicyclic ring system. Alicyclic systems are optionally substituted.

The term "aryl" preferably refers to an aromatic monocyclic ring containing 6 carbon atoms, an aromatic bicyclic ring system containing 10 carbon atoms or an aromatic tricyclic ring system containing 14 carbon atoms. Examples are phenyl, naphtyl or anthracenyl. The aryl group is optionally substituted. The term "heteroaryl" preferably refers to a five or six-membered aromatic monocyclic ring wherein at least one of the carbon atoms are replaced by 1, 2, 3, or 4 (for the five membered ring) or 1, 2, 3, 4, or 5 (for the six membered ring) of the same or different heteroatoms, preferably selected from O, N and S; an aromatic bicyclic ring system wherein 1, 2, 3, 4, 5, or 6 carbon atoms of the 8, 9, 10, 11 or 12 carbon atoms have been replaced with the same or different heteroatoms, preferably selected from O, N and S; or an aromatic tricyclic ring system wherein 1, 2, 3, 4, 5, or 6 carbon atoms of the 13, 14, 15, or 16 carbon atoms have been replaced with the same or different heteroatoms, preferably selected from O, N and S. Examples are oxazolyl, isoxazolyl, 1,2,5- oxadiazolyl, 1,2,3-oxadiazolyl, pyrrolyl, imidazolyl, pyrazolyl, 1,2,3-triazolyl, thiazolyl, isothiazolyl, 1,2,3,-thiadiazolyl, 1,2,5-thiadiazolyl, pyridinyl, pyrimidinyl, pyrazinyl, 1,2,3-triazinyl, 1,2,4-triazinyl, 1,3,5-triazinyl, 1-benzofuranyl, 2-benzofuranyl, indolyl, isoindolyl, benzothiophenyl, 2-benzothiophenyl, lH-indazolyl, benzimidazolyl, benzoxazolyl, indoxazinyl, 2,1-benzisoxazoyl, benzothiazolyl, 1,2-benzisothiazolyl, 2,1-benzisothiazolyl, benzotriazolyl, quinolinyl, isoquinolinyl, quinoxalinyl, quinazolinyl, 1,2,3-benzotriazinyl, or 1,2,4-benzotriazinyl.

The terms "alkenyl" and "cycloalkenyl" refer to olefinic unsaturated carbon atoms containing chains or rings with one or more double bonds. Examples are propenyl and cyclohexenyl. Preferably, the alkenyl chain comprises from 2 to 8 carbon atoms, i.e. 2, 3, 4, 5, 6, 7, or 8, e.g. ethenyl, 1 -propenyl, 2-propenyl, z^'so-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, iso- butenyl, sec-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, hexenyl, heptenyl, octenyl. The term also comprises CH₂, i.e. methenyl, if the substituent is directly bonded via the double bond. Preferably the cycloalkenyl ring comprises from 3 to 14 carbon atoms, i.e. 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13 or 14, e.g. cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, eye lo heptenyl, cyclooctyl, cyclononenyl, cyclodecenyl, spiro[3,3]heptenyl, spiro[3,4]octenyl, spiro[4,3]octenyl, spiro[3,5]nonenyl, spiro[5,3]nonenyl, spiro[3,6]decenyl, spiro[6,3]decenyl, spiro[4,5]decenyl, spiro[5,4]decenyl, bicyclo[4.1.0]heptenyl, bicyclo[3.2.0]heptenyl, bicyclo[2.2.1]heptenyl, bicyclo[2.2.2]octenyl, bicyclo[5.1.0]octenyl, bicyclo[4.2.0]octenyl, hexahydro-pentalenyl, hexahydro-indenyl, octahydro-azulenyl, or octahydro-naphthalenyl.

The term "alkynyl" refers to unsaturated carbon atoms containing chains or rings with one or more triple bonds. An example is the propargyl radical. Preferably, the alkynyl chain comprises from 2 to 8 carbon atoms, i.e. 2, 3, 4, 5, 6, 7, or 8, e.g. ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-pentynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, hexynyl, pentynyl, octynyl.

The term "optionally substituted" in each instance if not further specified refers to between 1 and 10 substituents, e.g. 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 substituents which are in each instance independently selected from the group consisting of halogen, in particular F, CI, Br or I; -R', -N0₂, -CN, -OR^*, -NR'R", -COOR', -CONR'R", -NR" 'COR"", -NR" 'COR"", -NR" 'CONR'R",

-NR"S0₂A, -COR' "; -S0₂NR'R", -OOCR' ", -CR" 'R" "OH, R' "OH, and -E;

R' and R' ' is each independently selected from the group consisting of hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, and aralkyl or together form a heteroaryl, or heterocycloalkyl;

R' " and R"" is each independently selected from the group consisting of hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, heterocycloalkyl, alkoxy, aryl, aralkyl, heteroaryl, and -NR'R";

E is selected from the group consisting of alkyl, alkenyl, cycloalkyl, alkoxy, alkoxyalkyl, heterocycloalkyl, an alicyclic system, aryl and heteroaryl; optionally substituted.

In a first aspect the present invention provides an improved anode composition for use in a lithium ion battery comprising a heteroaromatic salt and a lithium ion intercalating compound. The present inventor surprisingly found that the inclusion of a heteroaromatic salt in the composition improves capacity in particular at high discharge rates. Preferably, the heteroaromatic salt comprises a heteroatom selected from the group consisting of O, S, Se, and Te, preferably Se or Te and most preferably Se.

In a preferred embodiment of the anode composition of the present invention the heteroaromatic salt is a pyrylium salt or pyridinium salt or derivative thereof. Preferably, the pyrylium salt or pyridinium salt comprises a heteroatom selected from the group consisting of O, S, Se, and Te, preferably Se or Te and most preferably Se.

In a preferred embodiment of the anode composition of the present invention the cation of the pyrylium salt has a structure according to formula (I)

wherein X is selected from the group consisting of O, S, Se, and Te, preferably Se or Te, most preferably Se;

Ri and R₃ are independently selected from H, alkyl, preferably Ci-C₆ alkyl, i.e. Ci, C₂, C₃, C₄, C₅, or C₆ alkyl, preferably methyl, ethyl, propyl, z^'so-propyl, butyl, z^'so-butyl, tert-butyl, pentyl or hexyl; alkenyl, e.g. C₂-Cs alkenyl, i.e. C₂, C₃, C₄, C₅, C₆, C₇, or Cs alkenyl, preferably ethenyl, 1-propenyl, 2-propenyl, z^'so-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, z^'so-butenyl, sec-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, hexenyl, heptenyl, octenyl; alkynyl, e.g. C₂-Cs alkynyl, i.e. C₂, C₃, C₄, C₅, C₆, C₇, or Cs alkynyl, preferably ethynyl, 1- propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-pentynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, hexynyl, pentynyl, octynyl; cycloalkyl, heterocycloalkyl, an alicyclic system, aryl, preferably a monocyclic, bicyclic or tricyclic aromatic ring, preferably phenyl, naphtyl or anthracenyl; heteroaryl, preferably a monocyclic, bicyclic or tricyclic heteroaromatic ring, more preferably oxazolyl, isoxazolyl, 1,2,5-oxadiazolyl, 1,2,3-oxadiazolyl, pyrrolyl, imidazolyl, pyrazolyl, 1,2,3-triazolyl, thiazolyl, isothiazolyl, 1,2,3,-thiadiazolyl, 1,2,5- thiadiazolyl, pyridinyl, pyrimidinyl, pyrazinyl, 1,2,3-triazinyl, 1 ,2,4-triazinyl, 1 ,3,5-triazinyl,

1- benzofuranyl, 2-benzofuranyl, indolyl, isoindolyl, benzothiophenyl, 2-benzothiophenyl, lH-indazolyl, benzimidazolyl, benzoxazolyl, indoxazinyl, 2,1-benzisoxazoyl, benzothiazolyl, 1,2-benzisothiazolyl, 2,1-benzisothiazolyl, benzotriazolyl, quinolinyl, isoquinolinyl, quinoxalinyl, quinazolinyl, 1,2,3-benzotriazinyl, or 1 ,2,4-benzotriazinyl; most preferred is aryl, optionally substituted;

R₂ is H, alkyl, preferably Ci-C₆ alkyl, i.e. Ci, C₂, C₃, C₄, C₅, or C₆ alkyl, preferably methyl, ethyl, propyl, z^'so-propyl, butyl, z^'so-butyl, tert-butyl, pentyl or hexyl; alkenyl, e.g. C₂-Cs alkenyl, i.e. C₂, C₃, C₄, C₅, C₆, C₇, or Cs alkenyl, preferably ethenyl, 1-propenyl, 2-propenyl, z^'so-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, z^'so-butenyl, sec-butenyl, 1-pentenyl, 2- pentenyl, 3-pentenyl, 4-pentenyl, hexenyl, heptenyl, octenyl; alkynyl, e.g. C₂-Cs alkynyl, i.e. C₂, C₃, C₄, C₅, C₆, C₇, or Cs alkynyl, preferably ethynyl, 1-propynyl, 2-propynyl, 1-butynyl,

2- butynyl, 3-butynyl, 1-pentynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, hexynyl, pentynyl, octynyl; cycloalkyl, heterocycloalkyl, an alicyclic system, aryl, preferably a monocyclic, bicyclic or tricyclic aromatic ring, preferably phenyl, naphtyl or anthracenyl; heteroaryl, preferably a monocyclic, bicyclic or tricyclic heteroaromatic ring, more preferably oxazolyl, isoxazolyl, 1,2,5-oxadiazolyl, 1,2,3-oxadiazolyl, pyrrolyl, imidazolyl, pyrazolyl, 1,2,3- triazolyl, thiazolyl, isothiazolyl, 1,2,3,-thiadiazolyl, 1,2,5-thiadiazolyl, pyridinyl, pyrimidinyl, pyrazinyl, 1,2,3-triazinyl, 1 ,2,4-triazinyl, 1,3,5-triazinyl, 1-benzofuranyl, 2- benzofuranyl, indolyl, isoindolyl, benzothiophenyl, 2-benzothiophenyl, lH-indazolyl, benzimidazolyl, benzoxazolyl, indoxazinyl, 2,1-benzisoxazoyl, benzothiazolyl, 1,2- benzisothiazolyl, 2,1-benzisothiazolyl, benzotriazolyl, quinolinyl, isoquinolinyl, quinoxalinyl, quinazolinyl, 1,2,3-benzotriazinyl, or 1,2,4-benzotriazinyl; most preferred is aryl, optionally substituted;

and at least one of Ri, R₂ and R₃ is not H.

In a preferred embodiment of the anode composition of the present invention Ri and R₃ are independently selected from phenyl, naphtyl and anthracenyl, optionally substituted; most preferably a phenyl. In a particularly preferred embodiment Ri and R₃ are identical, preferably both are phenyl. The phenyl, naphtyl and anthracenyl can be optionally substituted.

Preferred substituents of the aryl are halogen, in particular F, CI, Br or I; -R', N0₂, CN, OR, -NR'R", COOR', -CONR'R", -NR" 'COR" ", NR" 'COR" ", NR" 'CONR'R", NR"S02A, -COR" '; -S02NR'R", -OOCR" ', CR" 'R" "OH, R" 'OH, and E;

R' " and R" " is each independently selected from the group consisting of hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, heterocycloalkyl, alkoxy, aryl, aralkyl, heteroaryl, and -NR'R";

The most preferred substituent is -COR" '. In this it is particularly preferred that the substituent is alkoxy.

In a preferred embodiment of the anode composition of the present invention R₂ is selected from phenyl, naphtyl and anthracenyl, optionally substituted; most preferably a phenyl.

In cases when R₂ is aryl; Preferred substituents of the aryl are halogen, in particular F, CI, Br or I; -R', N0₂, CN, OR, -NR'R", COOR', -CONR'R", -NR" 'COR" ", NR" 'COR" ", NR" 'CONR'R", NR"S02A, -COR' "; -S02NR'R", -OOCR' ", CR" 'R" "OH, R" 'OH, and E;

The most preferred substituent is -COR" '. In this it is particularly preferred that the substituent is alkoxy. Preferably the substitution is in para position.

Accordingly, in preferred embodiments the cation of the heteroaromatic salt of the present invention has a structure according to formula (III)

(III)

wherein R₂ has the meaning and preferred meanings outlined above, in particular is 4- alkoxy-phenyl, e.g. 4-methoxy-alkyl.

In a preferred embodiment of the anode composition of the present invention the anion of the heteroaromatic salt is selected from a halide; halate, preferably fluorate, chlorate, bromate, iodate; perhalate, preferably perfluorate, perchlorate, perbromate, or periodate; sulphate, carbonate, preferably F , CI , Br and I , most preferably Br .

In a preferred embodiment of the anode composition of the present invention the heteroaromatic salt further comprises an addition salt, preferably selected from a Mn, Fe, Co, Ni, Cu, Zn, Be, Mg, Ca, Sr, B, Al, Ga, V, Cd, Hg, Ag, Mo, W, Ti, Cr, Sn, Pb, and Ba salt or mixtures thereof, preferably a Zn salt.

In a preferred embodiment of the anode composition of the present invention the addition salt is a halide, preferably F , CI , Br and I , most preferably Br ; halate; preferably fluorate, chlorate, bromate, iodate perhalate, preferably perfluorate, perchlorate, perbromate, or periodate; sulphate, carbonate, preferably fluoride, chloride, bromide, or iodide.

Particularly preferred addition salts are ZnCl₂, ZnBr₂, and ZnF₂, most preferably ZnBr₂.

The molar ratio of the addition salt and the heteroaromatic salt is between 0.1 to 1.0, i.e. 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, and 1.0, preferably about 0.5.

Accordingly, in a particular preferred embodiment the heteroaromatic salt of the present invention has a structure according to Formula (IV)

0.5 ZnBr₂

(IV)

wherein R₂ has the meaning and preferred meanings outlined above, in particular is 4- methoxy-phenyl. In a preferred embodiment of the anode composition of the present invention the lithium ion intercalating compound is selected from the group consisting of mesophase carbon microbeads (MCMB), graphite, vapor grown carbon fiber (VGCF), carbon nano-tube (CNT), coke, carbon black (CB), graphene, acetylene black (AB), carbon fiber, and glassy carbon or mixtures thereof. Particularly preferred is graphene. Preferably, the graphene has a purity of at least 95%, more preferably of at least 96%, more preferably of at least 97%, more preferably of at least 98%, more preferably of at least 99%, and more preferably of at least 99.9%.

In a preferred embodiment of the anode composition of the present invention the heteroaromatic salt is comprised in an amount ranging from 5 to 50 weight%>, i.e. 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 , 22, 23, 24, 25,2 6,2 7, 28, 29, 30, 31 , 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, or 50 weight% on the basis of the weight of the total anode composition material. Preferred ranges are between 10 to 40 weight%, more preferably between 15 to 35 weight%>, most preferably about 30 weight%>.

In a preferred embodiment of the anode composition of the present invention the lithium ion intercalating compound is comprised in an amount ranging from 30 to 95 weight%>, i.e. 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67 ,68, 69, 70, 71 , 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, or 95 weight% on the basis of the weight of the total anode composition. Preferred ranges are between 40 to 90 weight%, more preferably between 50 to 70 weight%>, most preferably about 60 weight%>.

In a preferred embodiment of the anode composition of the present invention it further comprises a soluble binder.

It is preferred that the soluble binder is selected from the group consisting of (polystyrenebutadienerubber)-poly (acrylonitrile-co-acrylamide), polyvinyledene fluoride (PVDF), ethylene-propylene and a diene (EPDM), or a compound according formula (II)

(II)

wherein

P is selected from the group comprising H, alkyl, preferably Ci-C₆ alkyl, i.e. Ci, C₂, C₃, C₄, C₅, or C₆ alkyl, preferably methyl, ethyl, propyl, z^'so-propyl, butyl, z^'so-butyl, tert-butyl, pentyl or hexyl; alkenyl, e.g. C₂-Cs alkenyl, i.e. C₂, C₃, C₄, C₅, C₆, C₇, or Cs alkenyl, preferably ethenyl, 1- propenyl, 2-propenyl, z^'so-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, z^'so-butenyl, sec-butenyl, 1- pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, hexenyl, heptenyl, octenyl; alkynyl, e.g. C₂-Cs alkynyl, i.e. C₂, C₃, C₄, C₅, C₆, C₇, or Cs alkynyl, preferably ethynyl, 1-propynyl, 2-propynyl, 1- butynyl, 2-butynyl, 3-butynyl, 1-pentynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, hexynyl, pentynyl, or octynyl;

R₅ and are independently selected from H, an aliphatic hydrocarbon group, aryl or heteroarly or are joined to form an aliphatic, aromatic, or heteroaromatic ring, preferably H; and n is an integer from 10 to 100.000, preferably an integer of more than 50, 100, 200, 300, 400, 500, 600, 700, 800, 900, 1,000, 2,000, 3.000, 4,000, 5000, 6,000, 7,000, 8,000, 9,000, 10,000, 15,000, 20,000, 25,000, 30,000, 35,000, 40,000, 45,000, 50,000, 55,000, 60,000, 65,000, 70,000, 75,000, 80,000, 85,000, 90,000, 95,000 or 100,000.

It is also preferred that both R5 and are identical.

In a preferred embodiment of the anode composition of the present invention the compound according to formula (II) is selected from the group consisting of polyacrylamide, poly-N- methylacrylamide, poly-N-ethylacrylamide, poly-N-isopropylacrylamide, poly-N,N- dimethylacrylamide, poly-N-acryloylpiperidine, poly-methacrylamide, poly-N- methylmethacrylamide, poly-N-ethylmethacryl amide, poly-N-isopropylmethacrylamide and poly- Ν,Ν-dimethylmethacrylamide, preferably polyacrylamide.

In the production of the anode composition with binder it is preferred that a solvent is used, which is capable of dissolving the respectively indicated binder. Preferred solvents are selected from nitromethane, esters and ethers, preferably nitromethane. The skilled person is capable of determining a suitable amount of solvent to dissolve the binder. In case of polyacrylamide a ratio of 5% solvent to 95% polyacrylamide is typically sufficient to dissolve the polyacrylamide.

In a preferred embodiment of the anode composition of the present invention the soluble binder is comprised in an amount ranging from 1 to 20 weight%, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 1 1, 12, 13, 14, 15, 16, 17, 18, 19 or 20 weight% on the basis of the weight of the total anode composition.

Preferred ranges are between 4 to 15 weight%, more preferably between 8 to 12 weight%, most preferably about 10 weight%.

In a preferred embodiment of the electrolyte of the present invention the heteroaromatic salt is a pyrylium salt or a pyridinium salt or a derivative thereof as described above. Preferably, the heteroaromatic salt comprises a heteroatom selected from the group consisting of O, S, Se, and Te, preferably Se or Te and most preferably Se.

In a preferred embodiment of the electrolyte of the present invention the heteroaromatic salt is a pyrylium salt or pyridinium salt or derivative thereof. Preferably, the pyrylium salt or pyridinium salt comprises a heteroatom selected from the group consisting of O, S, Se, and Te, preferably Se or Te and most preferably Se.

In a preferred embodiment of the electrolyte of the present invention the cation of the pyrylium salt has a structure according to formula (I)

wherein X is selected from the group consisting of O, S, Se, and Te, preferably Se or Te, most preferably;

Ri and R₃ are independently selected from H, alkyl, preferably Ci-C₆ alkyl, i.e. Ci, C₂, C₃, C₄, C₅, or C₆ alkyl, preferably methyl, ethyl, propyl, z^'so-propyl, butyl, z^'so-butyl, tert-butyl, pentyl or hexyl; alkenyl, e.g. C₂-Cs alkenyl, i.e. C₂, C₃, C₄, C₅, C₆, C₇, or Cs alkenyl, preferably ethenyl, 1-propenyl, 2-propenyl, z^'so-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, z^'so-butenyl, sec-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, hexenyl, heptenyl, octenyl; alkynyl, e.g. C₂-Cs alkynyl, i.e. C₂, C₃, C₄, C₅, C₆, C₇, or Cs alkynyl, preferably ethynyl, 1- propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-pentynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, hexynyl, pentynyl, octynyl; cycloalkyl, heterocycloalkyl, an alicyclic system, aryl, preferably a monocyclic, bicyclic or tricyclic aromatic ring, preferably phenyl, naphtyl or anthracenyl; heteroaryl, preferably a monocyclic, bicyclic or tricyclic heteroaromatic ring, more preferably oxazolyl, isoxazolyl, 1 ,2,5-oxadiazolyl, 1 ,2,3-oxadiazolyl, pyrrolyl, imidazolyl, pyrazolyl, 1 ,2,3-triazolyl, thiazolyl, isothiazolyl, 1 ,2,3,-thiadiazolyl, 1 ,2,5- thiadiazolyl, pyridinyl, pyrimidinyl, pyrazinyl, 1 ,2,3-triazinyl, 1 ,2,4-triazinyl, 1 ,3,5-triazinyl, 1-benzofuranyl, 2-benzofuranyl, indolyl, isoindolyl, benzothiophenyl, 2-benzothiophenyl, lH-indazolyl, benzimidazolyl, benzoxazolyl, indoxazinyl, 2, 1-benzisoxazoyl, benzothiazolyl, 1 ,2-benzisothiazolyl, 2, 1-benzisothiazolyl, benzotriazolyl, quinolinyl, isoquinolinyl, quinoxalinyl, quinazolinyl, 1 ,2,3-benzotriazinyl, or 1 ,2,4-benzotriazinyl; most preferred is aryl, optionally substituted; R₂ is H, alkyl, preferably Ci-C₆ alkyl, i.e. Ci, C₂, C₃, C₄, C₅, or C₆ alkyl, preferably methyl, ethyl, propyl, z^'so-propyl, butyl, z^'so-butyl, tert-butyl, pentyl or hexyl; alkenyl, e.g. C₂-Cs alkenyl, i.e. C₂, C₃, C₄, C₅, C₆, C₇, or Cs alkenyl, preferably ethenyl, 1-propenyl, 2-propenyl, z^'so-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, z^'so-butenyl, sec-butenyl, 1-pentenyl, 2- pentenyl, 3-pentenyl, 4-pentenyl, hexenyl, heptenyl, octenyl; alkynyl, e.g. C₂-Cs alkynyl, i.e. C₂, C₃, C₄, C₅, C₆, C₇, or Cs alkynyl, preferably ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-pentynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, hexynyl, pentynyl, octynyl; cycloalkyl, heterocycloalkyl, an alicyclic system, aryl, preferably a monocyclic, bicyclic or tricyclic aromatic ring, preferably phenyl, naphtyl or anthracenyl; heteroaryl, preferably a monocyclic, bicyclic or tricyclic heteroaromatic ring, more preferably oxazolyl, isoxazolyl, 1,2,5-oxadiazolyl, 1,2,3-oxadiazolyl, pyrrolyl, imidazolyl, pyrazolyl, 1,2,3- triazolyl, thiazolyl, isothiazolyl, 1,2,3,-thiadiazolyl, 1,2,5-thiadiazolyl, pyridinyl, pyrimidinyl, pyrazinyl, 1,2,3-triazinyl, 1,2,4-triazinyl, 1,3,5-triazinyl, 1-benzofuranyl, 2- benzofuranyl, indolyl, isoindolyl, benzothiophenyl, 2-benzothiophenyl, lH-indazolyl, benzimidazolyl, benzoxazolyl, indoxazinyl, 2,1-benzisoxazoyl, benzothiazolyl, 1,2- benzisothiazolyl, 2,1-benzisothiazolyl, benzotriazolyl, quinolinyl, isoquinolinyl, quinoxalinyl, quinazolinyl, 1,2,3-benzotriazinyl, or 1,2,4-benzotriazinyl; most preferred is aryl, optionally substituted;

and at least one of Ri, R₂ and R₃ is not H.

In a preferred embodiment of the electrolyte of the present invention Ri and R₃ are independently selected from phenyl, naphtyl and anthracenyl, optionally substituted; most preferably a phenyl. Most preferably Ri and R₃ are identical, preferably phenyl. The phenyl, naphtyl and anthracenyl can be optionally substituted.

Preferred substituents of the aryl are halogen, in particular F, CI, Br or I; -R', N0₂, CN,

OR, -NR'R", COOR', -CONR'R", -NR"'COR" ", NR" 'COR" ", NR" 'CONR'R",

NR"S02A, -COR"'; -S02NR'R", -OOCR"', CR"'R" "OH, R'"OH, and E;

R" ' and R" " is each independently selected from the group consisting of hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, heterocycloalkyl, alkoxy, aryl, aralkyl, heteroaryl, and -NR'R";

E is selected from the group consisting of alkyl, alkenyl, cycloalkyl, alkoxy, alkoxyalkyl, heterocycloalkyl, an alicyclic system, aryl and heteroaryl; optionally substituted. In a preferred embodiment of the electrolyte of the present invention R₂ is selected from phenyl, naphtyl and anthracenyl, optionally substituted, preferably by one or more alkoxy groups.

In a preferred embodiment of the electrolyte of the present invention R₂ is selected from phenyl, naphtyl and anthracenyl, optionally substituted, optionally substituted; most preferably a phenyl.

Preferred substituents of the aryl are halogen, in particular F, CI, Br or I; -R', N0₂, CN, OR, -NR'R", COOR', -CONR'R", -NR"'COR" ", NR" 'COR" ", NR" 'CONR'R", NR"S02A, -COR"'; -S02NR'R", -OOCR"', CR"'R" "OH, R' "OH, and E;

R'" and R" " is each independently selected from the group consisting of hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, heterocycloalkyl, alkoxy, aryl, aralkyl, heteroaryl, and -NR'R";

In a preferred embodiment of the electrolyte of the present invention R₂ is selected from phenyl, naphtyl and anthracenyl, optionally substituted, preferably by one or more alkoxy groups.

Accordingly, the cation has a structure according to formula (III)

(III)

In a preferred embodiment of the electrolyte of the present invention the anion of the heteroaromatic salt is selected from a halide; halate, preferably fluorate, chlorate, bromate, iodate; perhalate, preferably perfluorate, perchlorate, perbromate, or periodate; sulphate, carbonate, preferably F , CI , Br and I , most preferably Br . In a preferred embodiment of the electrolyte of the present invention the heteroaromatic salt further comprises an addition salt, preferably selected from a Mn, Fe, Co, Ni, Cu, Zn, Be, Mg, Ca, Sr, B, Al, Ga, V, Cd, Hg, Ag, Mo, W, Ti, Cr, Sn, Pb, and Ba salt or mixtures thereof, preferably a Zn salt.

In a preferred embodiment of the electrolyte of the present invention the addition salt is a halide, preferably F , CI , Br and I , most preferably Br ; halate; preferably fluorate, chlorate, bromate, iodate perhalate, preferably perfluorate, perchlorate, perbromate, or periodate; sulphate, carbonate, preferably fluoride, chloride, bromide, or iodide.

Particularly preferred addition salts are ZnCl₂, ZnBr₂, and ZnF₂, most preferably ZnBr.

Accordingly, in a particular preferred embodiment the heteroaromatic salt has a structure according to Formula (IV)

0.5 ZnBr₂

(IV)

wherein R₂ has the meaning and preferred meanings outlined above, in particular is 4- methoxy-phenyl.

In a preferred embodiment the electrolyte of the present invention further comprises a separator compound.

In a preferred embodiment of the electrolyte of the present invention the separator compound is selected from the group consisting of polyethylene, polypropylene, polycarbonate, fluorinated polymers and mixtures thereof.

In a preferred embodiment of the electrolyte of both aspects of the present invention the polysaccharide ester is selected from a ?-l,4-glucan ester (cellulose ester), -l,4-glucanan ester (amylose ester amylopectin ester), a -l,6-glucan ester (dextran ester), a ?-l,6-glucan ester (pustulan ester), ?-l,3-glucan ester, ?-l,4-galactan ester, ?-l,4-mannan, -l,6-mannan ester, pullulan ester, agarose ester and alginic acid ester, preferably cellulose ester.

In a preferred embodiment of the electrolyte of both aspects of the present invention the ester is an ester of an organic acid, preferably of a Ci to C₆ organic acid, more preferably of acetic acid, propionic acid, butyric acid or a mixture thereof.

In a preferred embodiment of the electrolyte of both aspects of the present invention the cellulose ester is selected from cellulose acetate, cellulose triacetate, cellulose propionate, cellulose acetate propionate, cellulose butyrate, cellulose acetate butyrate, and cellulose sulphate.

In a preferred embodiment of the electrolyte of both aspects of the present invention the polysaccharide ester is comprised in an amount ranging from 60 to 95 weight%, i.e. 60, 61, 62, 63, 64, 65, 66, 67 ,68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, or 95 weight% on the basis of the weight of the total electrolyte. Preferred ranges are between 70 to 90 weight%, more preferably between 80 to 88 weight%, most preferably about 85 weight%.

Preferably, the components of the electrolyte of both aspects of the present invention are selected in such that the electrolyte is capable of forming a solid sheet or film like structure. This is affected by appropriately selecting the amount of separator comprised in the electrolyte.

In the preferred embodiment, wherein the electrolyte of both aspects of the invention is in the form of a sheet or film it has a thickness of between 10 to 200 μιη, e.g. 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 110, 120, 130, 140, 150, 160, 170 180, 190 or 200 μιη. Preferred ranges are between 15 to 100 μιη, more preferably between 20 to 80 μιη and most preferably between 25 to 50 μιη. Similarly, thicknesses are preferably be obtained, when a solution or dispersion of the electrolyte is coated onto a cathode and/or anode.

In those embodiments of the present invention, wherein the electrolyte of both aspects of the invention also comprises a separator compound it also functions as a separator.

In a preferred embodiment the electrolyte of both aspects of the invention further comprises an electrolytic salt.

In a preferred embodiment of the electrolyte of both aspects of the present invention the electrolytic salt is selected from a lithium salt such as lithium perchlorate (LiC10₄), lithium hexafluorophosphate (LiPF₆), lithium borofluoride (LiBF₄), lithium hexafluoroarsenide (LiAsF₆), lithium trifluoro-metasulfonate (L1CF3SO3) and bis-trifluoromethyl sulfonylimide lithium (Li (CF3S02)2), an a heteroaromatic salt.

In a preferred embodiment of the electrolyte of both aspects of the present invention the electrolytic salt is comprised in an amount ranging from 1 to 20 weight%, i.e. 1 , 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20 weight%, on the basis of the weight of the total electrolyte. Preferred ranges are between 2 to 15 weight%, more preferably between 4 to 10 weight%, most preferably about 6 weight%.

In a preferred embodiment of the electrolyte of both aspects of the present invention the non-aqueous solvent is selected from the group consisting of dimethyl carbonate (DMC), methylethyl carbonate (MEC), diethyl carbonate (DEC), ethyl propionate, methyl propionate, propylene carbonate (PC), γ-butyro lactone (γ-BL), acetonitrile (AN), ethyl acetate (EA), propyl formate (PF), methyl formate (MF), toluene, xylene and methyl acetate (MA) or mixtures thereof.

The non-aqueous solvent is preferably a mixture solvent of two types of solvents, wherein the first type solvent has a high dielectric constant and a high viscosity, and the second type solvent has a relatively lower dielectric constant and a relatively lower viscosity; wherein the first type solvent is selected from the group consisting of ethylene carbonate (EC), propylene carbonate (PC), butylene carbonate, dipropyl carbonate, acid anhydride, N-methylpyrrolidone, N-methyl acetamide, N-methyl formamide, dimethyl formamide, y-butyrolactone, acetonitrile, dimethyl sulfoxide and dimethyl sulfite; and the second type solvent is selected from the group consisting of ether, ester, and carbonate; wherein the ether is selected from the group consisting of 1 ,2-diethoxyethane, 1,2- dimethoxyethane, 1 ,2-dibutoxyethane, tetrahydrofuran, 2-methyl tetrahydrofuran, and propylene oxide; the ester is selected from the group consisting of methyl acetate, ethyl acetate, methyl butyrate, ethyl butyrate, methyl proionate, and ethyl propionate; and the carbonate is selected from the group consisting of dimethyl carbonate (DMC), diethyl carbonate (DEC) and ethyl methyl carbonate (EMC). The most preferred combination is of PC and dimethoxy ethane. Preferably, the first and second solvent are mixed in equal ratios by volume.

In a preferred embodiment of the electrolyte of both aspects of the present invention the non-aqueous solvent or mixtures thereof are comprised in an amount ranging from 0.5 to 10 weight%, i.e. 0.5, 0.6, 0.7, 0.8, 0.9, 1 , 1.1., 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.5, 3, 4, 5, 6, 7, 8, 9, or 10 weight%, on the basis of the weight of the total electrolyte. Preferred ranges are between 1 to 10 weight%, more preferably between 1 to 2.5 weight%, most preferably about 1.9 weight%.

The electrolyte of the present invention preferably also acts as a separator.

(b) a electrolyte; and

(c) a cathode.

(a) an anode comprising an anode composition according to the present invention; (b) a electrolyte; and

(c) a cathode comprising a cathode composition,

wherein the cathode is producible by a process comprising the steps:

(ii) applying the mixture to an cathode current collector; and

(iii) evaporating the solvent.

In a sixth aspect the present invention relates to a to a lithium ion battery comprising

(a) an anode,

(b) a electrolyte according to of the present invention; and

(c) a cathode comprising a cathode composition,

wherein the cathode is producible by a process comprising the steps:

(ii) applying the mixture to an cathode current collector; and

(iii) evaporating the solvent.

It is preferred in the fifth and sixth aspect of the lithium ion battery of the present invention that the lithium salt is selected from the group lithium oxide, lithium carbonate, lithium nitrate, lithium halide and mixtures thereof. Most preferably the lithium salt is lithium carbonate.

In a preferred embodiment the lithium salt is comprised in an amount ranging from 30 to 80 weight%, i.e. 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67 , 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, or 80 weight%, on the basis of the weight of the total cathode composition. Preferred ranges are between 40 to 75 weight%, more preferably between 50 to 70 weight%, most preferably about 65 weight%.

It is preferred in the fifth and sixth aspect of the lithium ion battery of the present invention that the transition metal is selected from the group consisting of Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Mo and alloys thereof, is preferably Co.

In a preferred embodiment the transition metal is comprised in an amount ranging from 10 to 40 weight%, i.e. 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39 or 40 weight%, on the basis of the weight of the total cathode composition. Preferred ranges are between 15 to 35 weight%, more preferably between 20 to 30 weight%, most preferably about 25 weight%. It is preferred in the fourth to sixth aspect of the lithium ion battery of the present invention that the organic polymer is selected from the group consisting of polystyrenebutadienerubber)-poly (acrylonitrile-co-acrylamide), polyvinyledene fluoride (PVDF), ethylene-propylene and a diene (EPDM), or a compound according formula (II)

(II)

wherein

P4 is selected from the group comprising H, alkyl, preferably Ci-C₆ alkyl, i.e. Ci, C₂, C₃, C₄, C₅, or C₆ alkyl, preferably methyl, ethyl, propyl, z^'so-propyl, butyl, z^'so-butyl, tert-butyl, pentyl or hexyl; alkenyl, e.g. C₂-Cs alkenyl, i.e. C₂, C₃, C₄, C₅, C₆, C₇, or Cs alkenyl, preferably ethenyl, 1- propenyl, 2-propenyl, z^'so-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, z^'so-butenyl, sec-butenyl, 1- pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, hexenyl, heptenyl, octenyl; alkynyl, e.g. C₂-Cs alkynyl, i.e. C₂, C₃, C₄, C₅, C₆, C₇, or Cs alkynyl, preferably ethynyl, 1-propynyl, 2-propynyl, 1- butynyl, 2-butynyl, 3-butynyl, 1-pentynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, hexynyl, pentynyl, octynyl;

P 5 and P6 are independently selected from H, an aliphatic hydrocarbon group, aryl or heteroarly or are joined to form an aliphatic, aromatic, or heteroaromatic ring, preferably H; and n is an integer from 10 to 100.000, preferably an integer of more than 50, 100, 200, 300, 400, 500, 600, 700, 800, 900, 1,000, 2,000, 3.000, 4,000, 5000, 6,000, 7,000, 8,000, 9,000, 10,000, 15,000, 20,000, 25,000, 30,000, 35,000, 40,000, 45,000, 50,000, 55,000, 60,000, 65,000, 70,000, 75,000, 80,000, 85,000, 90,000, 95,000 or 100,000.

It is also preferred that both R5 and are identical.

It is particularly preferred that the organic polymer is selected from the group consisting of polyacrylamide, poly-N-methylacrylamide, poly-N-ethylacrylamide, poly-N-isopropylacrylamide, poly-N,N-dimethylacrylamide, poly-N-acryloylpiperidine, poly-methacrylamide, poly-N- methylmethacrylamide, poly-N-ethylmethacryl amide, poly-N-isopropylmethacrylamide and poly- Ν,Ν-dimethylmethacrylamide, preferably polyacrylamide.

In the production of the cathode a solvent is used to dissolve the organic polymer in an amount capable of dissolving the respective polymer. Preferred solvents are organic solvents, preferably selected from nitromethane, ether and esters. The skilled person is capable of determining a suitable amount of solvent to dissolve the organic polymer. In case of polyacrylamide a ratio of 5% solvent to 95% polyacrylamide is typically sufficient to dissolve the polyacrylamide.

In a preferred embodiment the cathode composition of the present invention comprises the organic polymer in an amount ranging from 1 to 20 weight%, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20 weight% on the basis of the weight of the total anode composition. Preferred ranges are between 4 to 15 weight%, more preferably between 8 to 12 weight%, most preferably about 10 weight%.

In a preferred aspect of the fourth to sixth aspect of the lithium ion battery the electrolyte is an electrolyte of the present invention.

(a) an anode;

(b) a electrolyte of the present invention; and

(c) a cathode.

In a preferred embodiment of the lithium ion battery according to the seventh aspect of the present invention the anode composition is an anode composition of the present invention.

In a preferred aspect the lithium ion battery of the present invention the cathode composition comprises a cathode active composition selected from the group consisting of lithium cobalt oxide, doped lithium cobalt oxide, lithium nickel oxide, doped lithium nickel oxide, lithium manganese oxide, doped lithium manganese oxide, lithium iron phosphate, lithium manganese phosphate, lithium vanadium oxide, doped lithium vanadium oxide, lithium vanadium phosphate, lithium transition metal phosphate, lithium mixed-metal phosphates, metal sulfides, metal phosphides, metal halogenides, and combinations thereof.

In a preferred aspect the lithium ion battery of the present invention the cathode composition further comprises a binder, preferably selected from the group consisting of polyethylene, polypropylene, polycarbonate, fluorinated polymers and combinations thereof.

In a preferred aspect the lithium ion battery of the present invention the cathode composition further comprises an electrically conductive additive, preferably selected from the group consisting of acetylene black, carbon black, graphite, nickel powder, aluminium powder, titanium powder, stainless steel powder, heteroaromatic salt and combinations thereof.

In all aspects of the lithium ion batteries of the present invention the cathode comprises a cathode current collector, preferably selected from the group consisting of Cu and Ti and alloys thereof, preferably Cu. Preferably, the cathode current collector has a sheet or rod like structure.

The cathode composition is preferably present on one or both surfaces of the cathode current collector with a thickness of between 1 to 40 μιη, e.g. 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 , 12, 13, 14, 15, 16, 17, 18, 19, 20, 25, 30, 35 or 40 μηι. Preferred ranges are between 2 to 30 μηι, more preferably between 3 to 20 μιη and most preferably about 15 μιη. This thickness is preferred for high power applications.

In an alternative preferred embodiment the cathode composition is present on one or both surfaces of the cathode current collector with a thickness of between 40 to 300 μιη, e.g. 40, 50, 60, 70, 80, 90. 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, 200, 210,220, 230, 240, 250, 260, 270, 280, 290 or 300 μιη. Preferred ranges are between 60 to 250 μιη, more preferably between 100 to 200 μιη and most preferably about 150 μιη. This thickness is preferred for high energy applications.

In all aspects of the lithium ion batteries of the present invention the anode comprises an anode current collector, preferably selected from the group consisting of Al, Mg, Ti and alloys thereof, preferably Al. Preferably, the anode current collector has a sheet or rod like structure.

The anode composition is preferably present on one or both surfaces of the anode current collector with a thickness of between 1 to 40 μιη, e.g. 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 , 12, 13, 14, 15, 16, 17, 18, 19, 20, 25, 30, 35 or 40 μιη. Preferred ranges are between 2 to 30 μιη, more preferably between 3 to 20 μιη and most preferably about 15 μιη. This thickness is preferred for high power applications in either discharging or charging for up to 150 C.

In an alternative preferred embodiment the anode composition is present on one or both surfaces of the anode current collector with a thickness of between 40 to 300 μιη, e.g. 40, 50, 60, 70, 80, 90. 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, 200, 210,220, 230, 240, 250, 260, 270, 280, 290 or 300 μιη. Preferred ranges are between 60 to 250 μιη, more preferably between 100 to 200 μιη and most preferably about 150 μιη. This thickness is preferred for high energy applications.

Examples

For the paste of the positive electrode a mixture of 25 parts per weight of metallic cobalt powder and 65 parts per weight lithium carbonate was prepared. 10 parts per weight of polyacrylamid gel consisting of 95% liquid poly aery lamide and 5%> nitromethane was added and mixed. The resulting mixture was coated in around a 35 μιη thick layer on each side of a copper foil. After one hour drying at room temperature the electrode was prepared to build in.

The negative electrode consist of a mixture of 30 parts per weight of selenopyrilium salt CisHisSeBr * 0.5 ZnBr₂ and of 60 parts per weight of graphite. 10 parts per weight of polyacrylamid gel consisting of 95%> liquid poly aery lamide and 5%> nitromethane was added and mixed. The resulting mixture was coated in around 40 μιη thick layer on each side of a aluminium foil. After one hour drying at room temperature the electrode was prepared to build in. Electrolyte and separator were made in one step. Just mixing 89.46 parts per weight acetone with 9.89 parts per weight Cellulose acetate and 0.68 parts per weight CisHisSeBr * 0.5 ZnBr₂ and 0.50 parts per weight propylene carbonate. The prepared mixture was poured into a glass form. After having been dried in the form at room temperature for half an hour, the film was taken out and in addition dried at room temperature for an additional hour. The thickness of the separator/ electrolyte film was 0.03 mm.

The electrodes were cut to a width of approximately 3 cm and in the length approximately of 1.5 m. On the positive copper foil and on the negative aluminium foil a tab was welded each at the beginning as conductor. 2 electrolyte/ separator films were cut to the same width but in the length to 1.65 m. The positive electrode was stacked with electrolyte/ separator and then with the negative electrode and finally with the second electrolyte/ separator. The stack was wounded to a prismatic cell with a length of 44 mm, a height of 9.4 mm and a width of 30 mm. The cell weight was 30 g. The capacity was about 2,050 mAh at a mean discharge voltage of 3.7 V. This results in a specific energy of about 250 Wh/kg and an energy density of roundabout 600 Wh/1. The peak discharge current was more than 210 A.

Claims

An anode composition for use in a lithium ion battery comprising an heteroaromatic salt and a lithium ion intercalating compound.

The anode composition according to claim 1, wherein the heteroaromatic salt is a pyrylium salt or a pyridinium salt or a derivative thereof.

The anode composition according to claims 1 and 2, wherein the cation of the pyrylium salt has a structure according to formula (I)

wherein X is selected from the group consisting of O, S, Se, and Te, preferably Se or Te;

Ri and R₃ are independently selected from H, alkyl, alkenyl, alkynyl, cycloalkyl, heterocycloalkyl, an alicyclic system, aryl or heteroaryl;

R₂ is H, alkyl, alkenyl, alkynyl, cycloalkyl, heterocycloalkyl, an alicyclic system, aryl or heteroaryl

and at least one of Ri, R₂ and R₃ is not H.

The anode composition according to claim 3, wherein Ri and R₃ are independently selected from phenyl, naphtyl and anthracenyl, optionally substituted.

The anode composition according to claim 3 or 4, wherein R₂ is selected from phenyl, naphtyl and anthracenyl, optionally substituted, preferably by one or more alkoxy groups.

The anode composition according to any of claims 1 to 5, wherein the anion of the heteroaromatic salt is selected from a halide, halate, perhalate, sulphate, carbonate, preferably F^", CI^", Br^"" and Γ.

7. The anode composition according to any of claims 1 to 6, wherein the heteroaromatic salt further comprises an addition salt, preferably selected from a Mn, Fe, Co, Ni, Cu, Zn, Be, Mg, Ca, Sr, B, Al, Ga, V, Cd, Hg, Ag, Mo, W, Ti, Cr, Sn, Pb, and Ba salt or mixtures thereof, preferably a Zn salt.

8. The anode composition according to claim 7, wherein the addition salt is a halide, halate, perhalate, sulphate, carbonate, preferably fluoride, chloride, bromide, or iodide. 9. The anode composition according to any of claims 1 to 8, wherein the lithium ion intercalating compound is selected from the group consisting of mesophase carbon microbeads (MCMB), graphite, vapor grown carbon fiber (VGCF), carbon nano-tube (CNT), coke, carbon black (CB), graphene, acetylene black (AB), carbon fiber, and glassy carbon or mixtures thereof.

10. The anode composition according to any of claims 1 to 9, wherein the heteroaromatic salt is comprised in an amount ranging from 5 to 50 weight% on the basis of the weight of the total anode composition. 11. The anode composition according to any of claims 1 to 10, wherein the lithium ion intercalating compound is comprised in an amount ranging from 30 to 95 weight% on the basis of the weight of the total anode composition.

12. The anode composition according to any of claims 1 to 11, further comprising a soluble binder.

13. The anode composition according to claim 12, wherein the soluble binder is selected from the group consisting of (polystyrenebutadienerubber)-poly (acrylonitrile-co-acrylamide), polyvinyledene fluoride (PVDF), ethylene-propylene and a diene (EPDM), or a compound according formula (II)

(II)

wherein

R4 is selected from the group comprising hydrogen, alkyl, alkenyl, alkynyl,

R₅ and R are independently selected from hydrogen, an aliphatic hydrocarbon group, aryl or heteroarly or are joined to form an aliphatic, aromatic or heteroaromatic ring; and

n is an integer from 100 to 100.000.

The anode composition according to claim 13, wherein the compound according to formula (II) is selected from the group consisting of polyacrylamide, poly-N-methylacrylamide, poly- N-ethylacrylamide, poly-N-isopropylacrylamide, poly-N,N-dimethylacrylamide, poly-N- acryloylpiperidine, poly-methacrylamide, poly-N-methylmethacrylamide, poly-N- ethylmethacryl amide, poly-N-isopropylmethacrylamide and poly-N,N- dimethylmethacrylamide, preferably polyacrylamide.

The anode composition according to any of claims 12 to 14, wherein the soluble binder is comprised in an amount ranging from 1 to 20 weight% on the basis of the weight of the total anode composition.

An electrolyte for use in a lithium ion battery comprising an electrolytic salt and a nonaqueous solvent, wherein the electrolytic salt is a heteroaromatic salt.

The electrolyte according to claim 16, wherein the heteroaromatic salt is a pyrylium salt or a pyridinium salt or a derivative thereof.

The electrolyte according to claim 16 or 17, wherein the cation of the pyrylium salt has a structure according to formula (I)

Ri and R₃ are independently selected from H alkyl, alkenyl, alkinyl, cycloalkyl, heterocycloalkyl, an alicyclic system, aryl or heteroaryl;

R₂ is H, alkyl, alkenyl, alkinyl, cycloalkyl, heterocycloalkyl, an alicyclic system, aryl or heteroaryl,

and at least one of Ri, R₂ and R₃ is not H.

19. The electrolyte according to claim 18, wherein Ri and R₃ are independently selected from phenyl, naphtyl or anthracenyl, optionally substituted.

20. The electrolyte according to claim 18 or 19, wherein R₂ is selected from phenyl, naphtyl or anthracenyl, optionally substituted, preferably by one or more alkoxy groups.

21. The electrolyte according to any of claims 16 to 20, wherein the anion of the heteroaromatic salt is selected from a halide, sulphate, halate, perhalate, carbonate, preferably F^", CI^", Br^" or T. 22. The electrolyte according to any of claims 16 to 21, wherein the heteroaromatic salt further comprises an addition salt, preferably selected from a Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Be, Mg, Ca, Sr, B, Al, Ga, Cd, Hg, Ag, Mo, W, Sn, Pb, and Ba salt.

23. The electrolyte according to any of claims 16 to 22, further comprising a separator compound.

24. The electrolyte according to claim 23, wherein the separator compound is selected from the group consisting of polyethylene, polypropylene, polycarbonate, fluorinated polymers and mixtures thereof.

25. An electrolyte for use in a lithium ion battery comprising a separator compound and a nonaqueous solvent, wherein the separator compound is a polysaccharide ester.

26. The electrolyte according to claim 25 wherein the polysaccharide ester is selected from a β- 1,4-glucan ester (cellulose ester), -l,4-glucanan ester (amylose ester amylopectin ester), a a- 1,6-glucan ester (dextran ester), a ?-l,6-glucan ester (pustulan ester), ?-l,3-glucan ester, β- 1,4-galactan ester, ?-l,4-mannan, -l,6-mannan ester, pullulan ester, agarose ester and alginic acid ester.

27. The electrolyte according to claim 25 or 26, wherein the ester is an ester of organic acid, preferably of acetic acid, propionic acid, butyric acid or a mixture thereof.

28. The electrolyte according to any of claims 25 to 27, wherein the polysaccharide ester is selected from cellulose acetate, cellulose triacetate, cellulose propionate, cellulose acetate propionate, cellulose butyrate, cellulose acetate butyrate, and cellulose sulphate. 29. The electrolyte according to claims 25 to 28, wherein the polysaccharide ester is comprised in an amount ranging from 60 to 95 weight% on the basis of the weight of the total electrolyte.

30. The electrolyte according to any of claims 25 to 29, further comprising an electrolytic salt. 31. The electrolyte according to claim 30, wherein the electrolytic salt is selected from a lithium salt such as lithium perchlorate (LiC10₄), lithium hexafluorophosphate (LiPF₆), lithium borofluoride (LiBF₄), lithium hexafluoroarsenide (LiAsF₆), lithium trifluoro-metasulfonate (L1CF3SO3) and bis-trifluoromethyl sulfonylimide lithium (LiN(CF₃S02)2), and a heteroaromatic salt.

32. The electrolyte according to any of claims 16 to 31, wherein the electrolytic salt is comprised in an amount ranging from 1 to 20 weight% on the basis of the weight of the total electrolyte.

33. The electrolyte according to claim 16 and 32, wherein the non-aqueous solvent is selected from the group consisting of dimethyl carbonate (DMC), methylethyl carbonate (MEC), diethyl carbonate (DEC), ethyl propionate, methyl propionate, propylene carbonate (PC), γ- butyrolactone (γ-BL), acetonitrile (AN), ethyl acetate (EA), propyl formate (PF), methyl formate (MF), toluene, xylene and methyl acetate (MA) or mixtures thereof. The electrolyte according to any of claims 16 to 33, wherein the non-aqueous solvent mixtures thereof are comprised in an amount ranging from 0.5 to 10 weight% on the basis the weight of the total electrolyte. 35. A lithium ion battery comprising:

(a) an anode comprising an anode composition according to claims 1 to 15,

(b) a electrolyte; and

(c) a cathode. 36. A lithium ion battery comprising

(a) an anode comprising an anode composition according to claims 1 to 15;

(b) a electrolyte; and

(c) a cathode comprising a cathode composition,

wherein the cathode is producible by a process comprising the steps:

(ii) applying the mixture to an cathode current collector; and

(iii) evaporating the solvent. 37. A lithium ion battery comprising

(a) an anode,

(b) a electrolyte according to claims 16 to 34; and

(c) a cathode comprising a cathode composition,

wherein the cathode is producible by a process comprising the steps:

(ii) applying the mixture to an cathode current collector; and

(iii) evaporating the solvent. 38. The lithium ion battery according to claim 36 or 37, wherein the lithium salt is selected from the group lithium oxide, lithium carbonate, lithium nitrate, lithium halide and mixtures thereof. The lithium ion battery according to any of claims 36 to 38, wherein the transition metal is selected from the group consisting of Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Mo and alloys thereof, preferably Co.

The lithium ion battery according to any of claims 34 to 39, wherein the polymer is selected from the group consisting of polystyrenebutadienerubber)-poly (acrylonitrile-co-acrylamide), polyvinyledene fluoride (PVDF), ethylene-propylene and a diene (EPDM), and a compound according formula (II)

(II)

wherein

P is selected from the group comprising hydrogen, alkyl, alkenyl, alkynyl,

P 5 and Re are independently selected from hydrogen, an aliphatic hydrocarbon group or an aromatic hydrocarbon group or are joined to form an cyclic aliphatic ring, aromatic or heteroaromatic ring; and

n is 100 to 10.000.

41. The lithium ion battery according to claim 40, wherein the compound according to formula (II) is selected from the group consisting of polyacrylamide, poly-N-methylacrylamide, poly- N-ethylacrylamide, poly-N-isopropylacrylamide, poly-N,N-dimethylacrylamide, poly-N- acryloylpiperidine, poly-methacrylamide, poly-N-methylmethacrylamide, poly-N- ethylmethacryl amide, poly-N-isopropylmethacrylamide and poly-N,N- dimethylmethacrylamide, preferably polyacrylamide. 42. The lithium ion battery according to any of claims 35 to 41, wherein the electrolyte is an electrolyte according to claims 16 to 34.

43. A lithium ion battery comprising

(a) an anode;

(b) a electrolyte according to claims 16 to 34; and (c) a cathode.

44. The lithium ion battery according to claim 43 wherein the anode composition is an anode composition according to claims 1 to 15.

45. The lithium ion battery according to any of claims 35 to 44, wherein the cathode composition comprises a cathode active composition selected from the group consisting of lithium cobalt oxide, doped lithium cobalt oxide, lithium nickel oxide, doped lithium nickel oxide, lithium manganese oxide, doped lithium manganese oxide, lithium iron phosphate, lithium manganese phosphate, lithium vanadium oxide, doped lithium vanadium oxide, lithium vanadium phosphate, lithium transition metal phosphate, lithium mixed-metal phosphates, metal sulfides, metal phosphides, metal halogenides, and combinations thereof.

46. The lithium ion battery according to any of claims 35 to 45, wherein the cathode composition further comprises a binder, preferably selected from the group consisting of polyethylene, polypropylene, polycarbonate, fluorinated polymers and combinations thereof.

47. The lithium ion battery according to any of claims 35 to 46, wherein the cathode composition further comprises an electrically conductive additive, preferably selected from the group consisting of acetylene black, carbon black, graphite, nickel powder, aluminium powder, titanium powder, stainless steel powder, heteroaromatic salt and combinations thereof.

48. The lithium ion battery according to any of claims 35 to 47, wherein the cathode comprises a cathode current collector, preferably selected from the group consisting of Cu and Ti and alloys thereof.

49. The lithium ion battery according to any of claims 35 to 48, wherein the anode comprises an anode current collector, preferably selected from the group consisting of Al, Mg, Ti and alloys thereof.