Solid material-/gel electrolyte accumulator with binder of inorganic-organic hybrid polymer and method for the production thereof

Patent metadata

Field	Value
Publication number	US-2016285099-A1
Application number	US-201314442636-A
Country	US
Kind code	A1
Filing date	Nov 19, 2013
Priority date	Nov 19, 2012
Publication date	Sep 29, 2016
Grant date	—

Abstract

The present invention relates to a lithium accumulator or a combination thereof with a double-layer capacitor which is distinguished by a solid material- or gel electrolyte and a binder made of inorganic-organic hybrid polymer. By means of the new binder concept presented here, it is possible to revolutionise the contacting of the individual components in these accumulators and thus to enable a fundamental improvement in the ion transport. Associated therewith is a new, fast, simple and flexible production method for lithium accumulators which optimises these with respect to safety, stability, environmental friendliness and efficiency.

First claim

1 . A rechargeable lithium battery, comprising
a) at least two electrodes, at least one of said two electrodes comprising a material selected from the group consisting of lithium-intercalating/-deintercalating substances and electrically conductive substances, and mixtures thereof; b) at least one solid material- and/or gel electrolyte which is disposed between the at least two electrodes; and c) at least one Li-ion-conducting binder with or without lithium salt which contacts the electrode material and/or the solid material- and/or gel electrolyte, wherein the binder comprises a lithium-ion-conductive,
inorganic-organic hybrid polymer, the solid material electrolyte consisting of particles which comprise Li-ion-conducting solid materials, and the gel electrolyte comprising Li-ion-conducting gels, and the electrode material comprising particles.

2 . (canceled)

3 . The rechargeable lithium battery according to claim 1 , wherein the binder
i) comprises a lithium salt, and/or ii) comprises metallically conducting or semiconducting additives for improving the electrical conductivity; and/or iii) degrades thermally only above 300° C.; and/or iv) has a modulus of elasticity of 10 kPa to 100 MPa; and/or v) has an electrochemical stability, measured relative to Pt and with LiCl 4 O 4 and with LiPF 6 , and also relative to Li(Mn,Ni) 7 O 4 and with LiPF 6 , up to above 5 V vs. Li/Li + .

4 . The rechargeable lithium battery according to claim 1 , wherein the inorganic-organic hybrid polymer comprises an inorganic-oxidic framework consisting of Si—O—Si bonds, this framework comprising optionally in addition
a) oxidic heteroatoms selected from the group consisting of Li, B, Zr, Al, Ti, Ge, P, As, Mg, Ca, Cr and W; and/or
b) organic substituents of vinyl, alkyl, acryl, methacryl, epoxy, PEG, aryl, styryl, (per)fluoroalkyl, (per)fluoroaryl, nitrile, isocyanate or organic carbonates and/or vinyl-, allyl-, acryl-, methacryl-, styrene-, epoxy- or cyanurate functionalities.

5 . (canceled)

6 . The rechargeable lithium battery according to claim 1 , wherein the electrode material of at least one of said at least two electrode is selected from the group consisting of carbons, alloys of Si, Li, Ge, Sn, Al, Sb, etc., Li 4 Ti 5 O 12 , Li 4−y A y Ti 5−x M x O 12 wherein A=Mg, Ca, Al; M=Ge, Fe, Co, Ni, Mn, Cr, Zr, Mo, V, Ta or a combination thereof, Li(Ni,Co,Mn)O 2 , Li 1+x (M,N) 1−x O 2 wherein M=Mn, Co, Ni or a combination thereof; N═Al, Ti, Fe, Cr, Zr, Mo, V, Ta, Mg, Zn, Ga, B, Ca, Ce, Y, Nb, Sr, Ba, Cd or a combination thereof, (Li,A) x (M,N) z O v−w X w wherein A=alkali, alkaline earth metal, lanthanoide or a combination thereof; M=Mn, Co, Ni or a combination thereof; N═Al, Ti, Fe, Cr, Zr, Mo, V, Ta, Mg, Zn, Ga, B, Ca, Ce, Y, Nb, Sr, Ba, Cd or a combination thereof; X═F, Si, LiFePO 4 , (Li,A)(M,B)PO 4 wherein A or B=alkali-, alkaline earth metal, lanthanoide or a combination thereof; M=Fe, Co, Mn, Ni, Ti, Cu, Zn, Cr or a combination thereof, LiVPO 4 F, (Li,A) 2 (M,B)PO 4 F wherein A or B=alkali-, alkaline earth metal, lanthanoide or a combination thereof; M=Fe, Co, Mn, Ni, Ti, Cu or a combination thereof, Li 3 V 2 PO 4 , Li(Mn,Ni) 2 O 4 , Li 1+x (M,N) 2−x O 4 wherein M=Mn; N═Co, Ni, Fe, Al, Ti, Cr, Zr, Mo, V, Ta or a combination thereof, and mixtures or combinations of the same.

7 .- 8 . (canceled)

9 . The rechargeable lithium battery according to claim 1 , wherein at least one electrode comprises no or at least one current conductor.

10 . The rechargeable lithium battery according to claim 1 , wherein at least one of said at least two electrodes and/or at least one solid material- and/or gel electrolyte comprises at least one lithium salt.

11 . (canceled)

12 . The rechargeable lithium battery according to claim 1 , wherein the lithium battery comprises
a) at least one double-layer capacitor; and/or b) a liquid electrolyte separator.

13 . (canceled)

14 . A method for the production of a lithium accumulator, in which
a) a sol made of an organically modified, polysiloxane-containing material is provided and is mixed with material, selected from the group consisting of lithium-intercalating/-deintercalating substances, electrically conductive substances and solid material electrolyte material and possibly with at least one organic solvent; b) the organic solvent is separated, material with a coating made of binder being produced; c) the material which now has a coating made of binder is isolated, dried and hardened; d) the coated material is compressed to form at least one electrode- and/or electrolyte layer or is processed with at least one solvent as paste and is processed to form at least one electrode- and/or electrolyte layer, and e) at least one solid material electrolyte and/or gel electrolyte is disposed between the at least one and at least one further electrode, respectively with or without current conductor, so that the electrolyte contacts the at least two electrodes.

15 . The method according to claim 14 , wherein, in step a), in addition at least one lithium salt and/or at least one hardener is added.

16 . The method according to claim 14 , wherein the electrode material of at least one electrode is selected from the group consisting of carbons, alloys of Si, Li, Ge, Sn, Al, Sb, etc., Li 4 Ti 5 O 12 , Li 4−y A y Ti 5−x M x O 12 wherein A=Mg, Ca, Al; M=Ge, Fe, Co, Ni, Mn, Cr, Zr, Mo, V, Ta or a combination thereof, Li(Ni,Co,Mn)O 2 , Li 1+x (M,N) 1−x O 2 wherein M=Mn, Co, Ni or a combination thereof; N═Al, Ti, Fe, Cr, Zr, Mo, V, Ta, Mg, Zn, Ga, B, Ca, Ce, Y, Nb, Sr, Ba, Cd or a combination thereof, (Li,A) x (M,N) z O v−w X w wherein A=alkali-, alkaline earth metal, lanthanoide or a combination thereof; M=Mn, Co, Ni or a combination thereof; N═Al, Ti, Fe, Cr, Zr, Mo, V, Ta, Mg, Zn, Ga, B, Ca, Ce, Y, Nb, Sr, Ba, Cd or a combination thereof; X═F, Si, LiFePO 4 , (Li,A)(M,B)PO 4 wherein A or B=alkali-, alkaline earth metal, lanthanoide or a combination thereof; M=Fe, Co, Mn, Ni, Ti, Cu, Zn, Cr or a combination thereof, LiVPO 4 F, (Li,A) 2 (M,B)PO 4 F wherein A or B=alkali-, alkaline earth metal, lanthanoide or a combination thereof; M=Fe, Co, Mn, Ni, Ti, Cu or a combination thereof, Li 3 V 2 PO 4 , Li(Mn,Ni) 2 O 4 , Li 1+x (M,N) 2−x O 4 wherein M=Mn; N═Co, Ni, Fe, Al, Ti, Cr, Zr, Mo, V, Ta or a combination thereof and mixtures or combinations of the same.

17 . The method according to claim 14 , wherein the solid material electrolyte comprises Li-ion-conducting solid materials and/or the gel electrolyte comprises Li-ion-conducting gels and/or the liquid electrolyte comprises Li-ion-conducting liquids.

18 . The method according to claim 14 , wherein the electrode material and/or the solid material electrolyte comprises particles.

19 . The method according to claim 14 , wherein the organic solvent is selected from the group consisting of organic solvents which dissolve the organically modified, polysiloxane-containing material.

20 . The method according to claim 14 , wherein
a) drying takes place at a temperature of 30 to 50° C. for 20 to 40 min; and/or b) hardening takes place at a temperature of 70 to 150° C. for 0.5 to 5 hours.

21 . (canceled)

22 . The rechargeable lithium battery according to claim 3 , wherein the lithium salt is selected from the group consisting of LiCl 4 O 4 , LiAlO 4 , LiAlCl 4 , LiPF 6 , LiBF 4 , LiBr, LiI, LiSCN, LiSbF 6 , LiAsF 6 , LiTfa, LiDFOB, LiBOB, LiTFSI, LiCF 3 SO 3 , LiC 4 F 9 SO 3 , LiN(CF 3 SO 2 ) 2 , LiN(C 2 F 5 SO 2 ) 2 ,

Assignees

• Fraunhofer Ges Forschung

Inventors

• Schulz Jochen
• Uebe Jochen
• Bittner Andreas
• Guntow Uwe
• Olsowski Birke-Elisabeth

Classifications

• H01M10/056

  characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes · CPC title

• H01M4/622 Primary

  being polymers · CPC title

• H01G11/56

  Solid electrolytes, e.g. gels; Additives therein · CPC title

• H01G11/84

  Processes for the manufacture of hybrid or EDL capacitors, or components thereof · CPC title

• H01M4/625

  Carbon or graphite · CPC title