Flame-Resistant High Energy Density Lithium-Ion Batteries and Manufacturing Method

1 . A lithium-ion battery comprising an anode, a cathode, and a lithium-ion permeable and electrically insulating separator that electrically separates the anode from the cathode, wherein the anode comprises (i) multiple particles of an anode active material, (ii) 0.1%-25% by weight of a first lithium ion-transporting medium, and (iii) from 5% to 80% by volume of pores in the anode, wherein

a) the first lithium ion-transporting medium and particles of the anode active material are combined to form an anode active material composite layer;

b) the anode active material occupies from 75% to 99.9% by weight of the anode; and

c) the first lithium ion-transporting medium comprises an ion-conducting or electron-conducting material selected from graphite, graphene, carbon, a sulfonated conducting polymer, a phthalocyanine compound, an organic or organometallic cathode or anode active material, or a combination thereof.

2 . The lithium-ion battery of claim 1 , wherein the anode comprises an anode active material selected from the group consisting of: (a) silicon (Si), germanium (Ge), tin (Sn), lead (Pb), antimony (Sb), phosphorus (P), bismuth (Bi), zinc (Zn), aluminum (Al), titanium (Ti), nickel (Ni), cobalt (Co), and cadmium (Cd); (b) alloys or intermetallic compounds of Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, Ti, Ni, Co, or Cd with other elements; (c) oxides, carbides, nitrides, sulfides, phosphides, selenides, and tellurides of Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, Ti, Fe, Ni, Co, V, or Cd, and their mixtures, composites, or lithium-containing composites; (d) salts and hydroxides of Sn; (e) lithium titanate, lithium manganate, lithium aluminate, lithium titanium niobate, lithium-containing titanium oxide, lithium transition metal oxide, ZnCo 2 O 4 ; (f) prelithiated versions thereof; and (g) combinations thereof.

3 . The lithium-ion battery of claim 1 , wherein the anode does not contain an additional conductive additive that is different than the graphite, graphene, or carbon and wherein the anode does not contain an inorganic solid electrolyte, a liquid electrolyte, a polymer gel electrolyte, or a solid polymer electrolyte.

4 . The lithium-ion battery of claim 1 , wherein the anode does not contain a binder resin therein and any binder resin, if present, is external to the anode and is between the anode and an anode current collector, acting to bond the anode and the anode current collector together.

5 . A lithium-ion battery comprising an anode, a cathode, and a lithium-ion permeable and electrically insulating separator that electrically separates the anode from the cathode, wherein the anode comprises (i) multiple particles of an anode active material and (ii) from 5% to 80% by volume of pores in the anode, wherein

a) the anode active material occupies from 75% to 100% by weight of the anode, not counting the weight of an anode current collector; and

b) the anode contains from 0% to 3% of a conductive additive, from 0% to 5% of a resin binder, and from 0% to 5% by weight of an electrolyte.

6 . The lithium-ion battery of claim 5 , wherein the anode contains no resin binder and no electrolyte and the anode active material is selected from the group consisting of silicon (Si), germanium (Ge), tin (Sn), lead (Pb), antimony (Sb), phosphorus (P), bismuth (Bi), zinc (Zn), aluminum (Al), titanium (Ti), nickel (Ni), cobalt (Co), cadmium (Cd), prelithiated versions thereof, and combinations thereof.

7 . The lithium-ion battery of claim 1 , wherein the cathode comprises no organic liquid electrolyte.

8 . The lithium-ion battery of claim 1 , wherein the cathode comprises a second solid-state lithium ion-transporting medium and a first cathode active material, wherein (i) the second lithium ion-transporting medium and particles of the first cathode active material are combined to form a cathode active material composite layer wherein the cathode active material occupies at least 75% by weight or by volume of the cathode composite layer; (ii) the second lithium ion-transporting medium comprises a material selected from graphite, graphene, carbon, a sulfonated conducting polymer, a phthalocyanine compound, an organic or organometallic cathode or anode active material, or a combination thereof, wherein the organic or organometallic cathode active material is different in composition than the first cathode active material; and (iii) the second lithium ion-transporting medium constitutes a 3D network of lithium ion-conducting paths or electron-conducting paths in the cathode.

9 . The lithium-ion battery of claim 8 , wherein the cathode does not contain an additional conductive additive that is different than the graphite, graphene, or carbon and wherein the cathode contains an inorganic solid electrolyte, a liquid electrolyte, a polymer gel electrolyte, or a solid polymer electrolyte.

10 . The lithium-ion battery of claim 1 , wherein the sulfonated conducting polymer comprises a sulfonated version of a conjugated polymer selected from Polyacetylene, Polythiophene, Poly(3-alkylthiophenes), Polypyrrole, Polyaniline, Poly(isothianaphthene), Poly(3,4-ethylenedioxythiophene) (PEDOT), alkoxy-substituted Poly(p-phenylene vinylene), Poly(2,5-bis(cholestanoxy) phenylene vinylene), Poly(p-phenylene vinylene), Poly(2,5-dialkoxy) paraphenylene vinylene, Poly[(1,4-phenylene-1,2-diphenylvinylene)], Poly(3′,7′-dimethyloctyloxy phenylene vinylene), Polyparaphenylene, Polyparaphenylene, Polyparaphenylene sulphide, Polyheptadiyne, Poly(3-hexylthiophene), Poly(3-octylthiophene), Poly(3-cyclohexylthiophene), Poly(3-methyl-4-cyclohexylthiophene), Poly(2,5-dialkoxy-1,4-phenyleneethynylene), Poly(2-decyloxy-1,4-phenylene), Poly(9,9-dioctylfluorene), Polyquinoline, a derivative thereof, a copolymer thereof, a lithiated version thereof, or a combination thereof.

11 . The lithium-ion battery of claim 1 , wherein the phthalocyanine compound selected from copper phthalocyanine, zinc phthalocyanine, tin phthalocyanine, iron phthalocyanine, lead phthalocyanine, nickel phthalocyanine, vanadyl phthalocyanine, fluorochromium phthalocyanine, magnesium phthalocyanine, manganous phthalocyanine, dilithium phthalocyanine, aluminum phthalocyanine chloride, cadmium phthalocyanine, chlorogallium phthalocyanine, cobalt phthalocyanine, silver phthalocyanine, a metal-free phthalocyanine, a chemical derivative thereof, a lithiated version thereof, or a combination thereof.

12 . The lithium-ion battery of claim 1 , wherein the organic or organometallic cathode or anode active material is selected from poly(anthraquinonyl sulfide) (PAQS), lithium oxocarbons, oxacarbon, 3,4,9,10-perylenetetracarboxylic dianhydride (PTCDA), poly(anthraquinonyl sulfide), pyrene-4,5,9,10-tetraone (PYT), polymer-bound PYT, Quino(triazene), redox-active organic material based on multiple adjacent carbonyl groups, Tetracyanoquinodimethane (TCNQ), tetracyanoethylene (TCNE), 2,3,6,7,10,11-hexamethoxytriphenylene (HMTP), poly(5-amino-1,4-dyhydroxy anthraquinone) (PADAQ), phosphazene disulfide polymer ([(NPS 2 ) 3 ]n), lithiated 1,4,5,8-naphthalenetetraol formaldehyde polymer, Hexaazatrinaphtylene (HATN), Hexaazatriphenylene hexacarbonitrile (HAT(CN)6), 5-Benzylidene hydantoin, Isatine lithium salt, Pyromellitic diimide lithium salt, tetrahydroxy-p-benzoquinone derivatives (THQLi 4 ), N,N′-diphenyl-2,3,5,6-tetraketopiperazine (PHP), N,N′-diallyl-2,3,5,6-tetraketopiperazine (AP), N,N′-dipropyl-2,3,5,6-tetraketopiperazine (PRP), a thioether polymer, a quinone compound, 1,4-benzoquinone, 5,7,12,14-pentacenetetrone (PT), 5-amino-2,3-dihydro-1,4-dyhydroxy anthraquinone (ADDAQ), 5-amino-1,4-dyhydroxy anthraquinone (ADAQ), calixquinone, Li 4 C 6 O 6 , Li 2 C 6 O 6 , Li 6 C 6 O 6 , Na 4 C 6 O 6 , Na 2 C 6 O 6 , Na 6 C 6 O 6 , tetralithium 1,2,4,5-benzenetetracarboxylate (Li 4 C 10 H 2 O 8 , Li 4 BTC) salt, tetralithium salt of tetrahydroxybenzoquinone (denoted Li 4 -THQ), tetralithium salt of dihydroxyterephthalate (Li 4 -p-DHT), Emodin (6-methyl1,3,8-trihydroxyanthraquinone), humic acid, dilithium salt of 2,5-(dianilino)terephthalate (denoted Li 2 — DAnT), Poly (2,2,6,6-tetramethylpiperdinyloxy4-yl methacrylate) (PTMA), tetralithium 2,5-dihydroxy-1,4-benzenedisulfonate, di-lithium (2,3-dilithium oxy)-terephthalate (denoted Li 4 -o-DHT), dilithium terephthalate, conjugated dicarboxylate, or a combination thereof.

13 . The lithium-ion battery of claim 12 , wherein the thioether polymer is selected from Poly[methanetetryl-tetra(thiomethylene)] (PMTTM), Poly(2,4-dithiopentanylene) (PDTP), or Poly(ethene-1,1,2,2-tetrathiol) (PETT), Poly(2-phenyl-1,3-dithiolane) (PPDT), Poly(1,4-di(1,3-dithiolan-2-yl)benzene) (PDDTB), poly(tetrahydrobenzodithiophene) (PTHBDT), poly[1,2,4,5-tetrakis(propylthio)benzene] (PTKPTB) having a polyphenylene main chain linking thiolane on benzene moieties as pendants, poly[3,4(ethylenedithio)thiophene](PEDTT) having polythiophene backbone linking cyclo-thiolane on the 3,4-position of the thiophene ring, or a combination thereof.

14 . The lithium-ion battery of claim 1 , wherein the first lithium ion-transporting medium further comprises a lithium salt dispersed therein.

15 . The lithium-ion battery of claim 8 , wherein the second lithium ion-transporting medium further comprises a lithium salt dispersed therein.

16 . The lithium-ion battery of claim 8 , wherein the first cathode active material is selected from lithium nickel manganese oxide (LiNi a Mn 2-a O 4 , 0<a<2), lithium nickel manganese cobalt oxide (LiNi n Mn m Co 1-n-m O 2 , 0<n<1, 0<m<1, n+m<1), lithium nickel cobalt aluminum oxide (LiNi c Co d Al 1-c-a O 2 , 0<c<1, 0<d<1, c+d<1), lithium manganate (LiMn 2 O 4 ), lithium iron phosphate (LiFePO 4 ), lithium manganese oxide (LiMnO 2 ), lithium cobalt oxide (LiCoO 2 ), lithium nickel cobalt oxide (LiNi p Co 1-p O 2 , 0<p<1), or lithium nickel manganese oxide (LiNi q Mn 2-q O 4 , 0<q<2).

17 . The lithium-ion battery of claim 8 , wherein the first cathode active material comprises an inorganic material selected from a metal oxide, metal phosphate, metal silicide, metal selenide, transition metal sulfide, or a combination thereof.

18 . The lithium-ion battery of claim 17 , wherein said inorganic material is selected from a lithium cobalt oxide, lithium nickel oxide, lithium manganese oxide, lithium vanadium oxide, lithium-mixed metal oxide, lithium iron phosphate, lithium manganese phosphate, lithium vanadium phosphate, lithium mixed metal phosphate, lithium metal silicide, or a combination thereof.

19 . The lithium-ion battery of claim 17 , wherein said inorganic material is selected from a metal fluoride or metal chloride including the group consisting of CoF 3 , MnF 3 , FeF 3 , VF 3 , VOF 3 , TiF 3 , BiF 3 , NiF 2 , FeF 2 , CuF 2 , CuF, SnF 2 , AgF, CuCl 2 , FeCl 3 , MnCl 2 , and combinations thereof.

20 . The lithium-ion battery of claim 17 , wherein said inorganic material is selected from a lithium transition metal silicate, denoted as Li 2 MSiO 4 or Li 2 Ma x Mb y SiO 4 , wherein M and Ma are selected from Fe, Mn, Co, Ni, V, or VO; Mb is selected from Fe, Mn, Co, Ni, V, Ti, Al, B, Sn, or Bi; and x+y<1.

21 . The lithium-ion battery of claim 17 , wherein said inorganic material is selected from a transition metal dichalcogenide, a transition metal trichalcogenide, or a combination thereof.

22 . The lithium-ion battery of claim 17 , wherein said inorganic material is selected from TiS 2 , TaS 2 , MoS 2 , NbSe 3 , MnO 2 , CoO 2 , an iron oxide, a vanadium oxide, or a combination thereof.

23 . The lithium-ion battery of claim 17 , wherein said inorganic material comprises a vanadium oxide selected from the group consisting of VO 2 , Li x VO 2 , V 2 O 5 , Li x V 2 O 5 , V 3 O 8 , Li x V 3 O 5 , Li x V 3 O 7 , V 4 O 9 , Li x V 4 O 9 , V 6 O 13 , Li x V 6 O 13 , their doped versions, their derivatives, and combinations thereof, wherein 0.1<x<5.

24 . The lithium-ion battery of claim 17 , wherein said inorganic material is selected from a layered compound LiMO 2 , spinel compound LiM 2 O 4 , olivine compound LiMPO 4 , silicate compound Li 2 MSiO 4 , Tavorite compound LiMPO 4 F, borate compound LiMBO 3 , or a combination thereof, wherein M is a transition metal or a mixture of multiple transition metals.

25 . The lithium-ion battery of claim 17 , wherein said inorganic material is selected from: (a) bismuth selenide or bismuth telluride, (b) transition metal dichalcogenide or trichalcogenide, (c) sulfide, selenide, or telluride of niobium, zirconium, molybdenum, hafnium, tantalum, tungsten, titanium, cobalt, manganese, iron, nickel, or a transition metal; (d) boron nitride, or (e) a combination thereof.

26 . A method of producing the lithium-ion battery of claim 1 , the method comprising:

a) Preparing an anode, a cathode, a lithium-ion permeable and electrically insulating separator, wherein the anode comprises from 10% to 80% by volume of pores in the anode and a composite comprising particles of an anode active material mixed with 0% to 25% by weight of a first lithium ion-transporting medium comprising a material selected from graphite, graphene, carbon, a sulfonated conducting polymer, a phthalocyanine compound, an organic or organometallic cathode or anode active material, or a combination thereof; and

b) combining the anode, the separator, the cathode, and a protective housing into the battery cell.

27 . The method of claim 26 , wherein the cathode comprises an inorganic solid electrolyte, an ionic liquid electrolyte, a polymer gel electrolyte, or a solid polymer electrolyte.

28 . The method of claim 1 , further including an anode current collector that supports the anode active material composite layer; wherein the anode active material occupies from 75% to 99.9% by weight of the anode, not counting the anode current collector weight.