Prelithiated Anode, Lithium-Ion Battery Containing Same, and Method of Producing Same
The disclosure provides a multi-layer prelithiated anode including (a) a conducting substrate having a first primary surface and a second primary surface; (b) a first layer of lithium metal deposited onto the first primary surface of the conducting substrate; (c) a first graphitic layer that substantially covers the first lithium metal layer; and (d) a first anode active layer deposited on a primary surface of the first graphitic layer. The first anode active layer includes an anode active material. Also provided are a lithium battery including such a prelithiated anode and a method of producing such an anode.
1 . A multi-layer prelithiated anode for a lithium-ion cell, said anode comprising:
a) a conducting substrate having a first primary surface and a second primary surface;
b) a first layer of lithium metal deposited onto or attached to the first primary surface of the conducting substrate;
c) a first graphitic layer that substantially covers the first lithium metal layer; and
d) a first anode active layer deposited on a primary surface of the first graphitic layer, wherein the first anode active layer includes an anode active material.
2 . The multi-layer prelithiated anode of claim 1 , wherein the first anode active layer includes multiple particles of an anode active material and a first binder that holds the multiple anode material particles together to form the first anode active layer.
3 . The multi-layer prelithiated anode of claim 2 , wherein the first anode active layer also includes a conductive additive and said first binder holds the multiple anode material particles and the conductive additive together to form the first anode active layer.
4 . The multi-layer prelithiated anode of claim 1 , wherein the first anode active layer includes a film including the anode active material.
5 . The multi-layer prelithiated anode of claim 1 , wherein the anode active material is selected from the group consisting of: (a) silicon (Si), germanium (Ge), phosphorus (P), tin (Sn), lead (Pb), antimony (Sb), 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-containing titanium oxide, lithium niobate, lithium transition metal oxide; (f) carbon or graphite particles; and (g) combinations thereof.
6 . The multi-layer prelithiated anode of claim 1 , wherein the anode active material is selected from silicon (Si), germanium (Ge), phosphorus (P), tin (Sn), SiOx (0<x<2.0), SnO 2 , or a combination thereof.
7 . The multi-layer prelithiated anode of claim 1 , wherein the first graphitic film includes a film, paper, or fabric layer of a graphene material, expanded graphite, recompressed exfoliated graphite, highly oriented pyrolytic graphite, polymer- or pitch-derived graphite, carbon nanotubes, carbon nano-fibers, carbon or graphite fibers, graphitic carbon, amorphous carbon, or a combination thereof.
8 . The multi-layer prelithiated anode of claim 7 , wherein the graphene material includes a material selected from pristine graphene, graphene oxide, reduced graphene oxide, graphene fluoride, graphene chloride, graphene bromide, graphene iodide, nitrogenated graphene, hydrogenated graphene, functionalized graphene, doped graphene, or a combination thereof.
9 . The multi-layer prelithiated anode of claim 1 , wherein the conducting substrate is selected from a solid metal film, a porous metal film, a graphitic film, or a combination thereof wherein the graphitic film includes a film, paper, or fabric of a graphene material, expanded graphite, recompressed exfoliated graphite, highly oriented pyrolytic graphite, polymer- or pitch-derived graphite, carbon nanotubes, carbon nano-fibers, carbon or graphite fibers, graphitic carbon, amorphous carbon, or a combination thereof.
10 . The multi-layer prelithiated anode of claim 1 , wherein the conducting substrate includes a thin film, paper, or fabric layer of a graphene material or a composite material including sheets of a graphene material dispersed in a polymer or metal matrix, wherein the graphene material is selected from pristine graphene, graphene oxide, reduced graphene oxide, graphene fluoride, graphene chloride, graphene bromide, graphene iodide, nitrogenated graphene, hydrogenated graphene, functionalized graphene, doped graphene, or a combination thereof.
11 . The multi-layer prelithiated anode of claim 1 , wherein the conducting substrate includes a thin solid film or porous layer of copper (Cu), nickel (Ni), or stainless steel having a thickness from 1 to 50 μm.
12 . The multi-layer prelithiated anode of claim 1 , further including (e) a second layer of lithium metal deposited onto the second primary surface of the conducting substrate; (f) a second graphitic layer that substantially covers the second lithium metal layer; and (g) a second anode active layer deposited on a primary surface of the second graphitic layer.
13 . The multi-layer prelithiated anode of claim 1 , wherein the first lithium metal layer contains a lithium amount sufficient to prelithiated the anode to a level of lithium interaction from 5% to 100% of the maximum lithium storage capacity in the anode active material.
14 . The multi-layer prelithiated anode of claim 1 , wherein the first lithium metal layer has a thickness from 10 nm to 100 μm.
15 . The multi-layer prelithiated anode of claim 1 , wherein the conductive substrate has a thickness from 1 to 50 μm.
16 . The multi-layer prelithiated anode of claim 1 , wherein the first graphitic layer has a thickness from 10 nm to 50 μm.
17 . A lithium-ion cell that includes the multi-layer prelithiated anode of claim 1 , a cathode, a separator that electrically isolates the anode from the cathode, and an electrolyte in ionic communication with the anode and the cathode.
18 . The lithium-ion cell of claim 17 , wherein said cathode active material is selected from an inorganic material, an organic material, a polymeric material, or a combination thereof.
19 . The lithium-ion cell of claim 18 , wherein said inorganic material is selected from a metal oxide, metal phosphate, metal silicide, metal selenide, transition metal sulfide, sulfur, lithium polysulfide, selenium, lithium selenide, or a combination thereof.
20 . The lithium-ion cell of claim 18 , 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.
21 . The lithium-ion cell of claim 18 , 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.
22 . The lithium-ion cell of claim 18 , 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, or V; Mb is selected from Fe, Mn, Co, Ni, V, Ti, Al, B, Sn, or Bi; and x+y≤1.
23 . The lithium-ion cell of claim 18 , wherein said inorganic material is selected from a transition metal dichalcogenide, a transition metal trichalcogenide, or a combination thereof.
24 . The lithium-ion cell of claim 18 , 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.
25 . The lithium-ion cell of claim 18 , wherein said metal oxide contains 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 8 , 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.
26 . The lithium-ion cell of claim 18 , wherein said metal oxide or metal phosphate 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.
27 . The lithium-ion cell of claim 18 , 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.
28 . The lithium-ion cell of claim 18 , wherein said organic material or polymeric material is selected from Poly(anthraquinonyl sulfide) (PAQS), a lithium oxocarbon, 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, 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 , or a combination thereof.
29 . The lithium-ion cell of claim 28 , wherein said thioether polymer is selected from Poly[methanetetryl-tetra(thiomethylene)] (PMTTM), Poly(2,4-dithiopentanylene) (PDTP), a polymer containing Poly(ethene-1,1,2,2-tetrathiol) (PETT) as a main-chain thioether polymers, a side-chain thioether polymer having a main-chain consisting of conjugating aromatic moieties, and having a thioether side chain as a pendant, 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, or poly[3,4(ethylenedithio)thiophene] (PEDTT).
30 . The lithium-ion cell of claim 18 , wherein said organic material contains a 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, or a combination thereof.
31 . The lithium-ion cell of claim 17 , wherein the anode includes Si that is prelithiated to approximately 60-100% and wherein the cathode includes a cathode active material that is initially lithium-free when the cell is made.
32 . A method of producing the multi-layer prelithiated anode of claim 1 , said method including: (A) providing a conducting substrate having a first primary surface and a second primary surface; (B) depositing a first layer of lithium metal onto the first primary surface of the conducting substrate; (C) depositing or attaching a first graphitic layer onto the first lithium metal layer wherein the first graphitic layer substantially covers the first lithium metal layer; and (D) depositing a first anode active layer on a primary surface of the first graphitic layer, wherein the first anode active layer includes an anode active material.
33 . The method of claim 32 , wherein the method is conducted in a roll-to-roll manner.
34 . The method of claim 32 , wherein step (B) includes a procedure selected from physical vapor deposition, chemical vapor deposition, sputtering, electrochemical deposition or plating, laser ablation-assisted deposition, plasma deposition, powder spraying of lithium, attaching a lithium foil, or a combination thereof.
35 . The method of claim 32 , wherein step (C) includes a procedure selected from spraying, casting, coating, printing, laminating, or a combination thereof.
36 . The method of claim 32 , wherein step (D) includes a procedure selected from spraying, casting, coating, printing, laminating, physical vapor deposition, chemical vapor deposition, sputtering, electrochemical deposition or plating, laser ablation-assisted deposition, plasma deposition, or a combination thereof.
37 . The method of claim 32 , wherein step (D) is conducted prior to step (C).