Anode protective layer comprising porous carbon particles doped with nitrogen and all solid- state battery comprising same

Abstract

Disclosed is an all-solid-state battery (ASSB) comprising an anode layer, an anode protective layer, a solid electrolyte layer, and a cathode layer in the order, wherein the anode protective layer comprises particles of a first lithiophilic material, spherical carbon particles and non-spherical carbon particles doped with nitrogen. In some embodiments, the non-spherical carbon particles further comprise particles of a second lithiophilic material distributed within the pores of or on surface thereof. In some embodiments, the ASSB comprising the anode protective layer exhibits an improved electrochemical performance.

Description

ANODE PROTECTIVE LAYER COMPRISING POROUS CARBON PARTICLES DOPED WITH NITROGEN AND ALL SOLID- STATE BATTERY COMPRISING SAMECROSS-REFERENCE[00011 The present application claims the benefit of US Serial No. 63 / 683,036, filed August 14, 2024, the entire content of which is incorporated herein by reference into this application.FIELD[0002[ The present disclosure is generally related to an anode protective layer for an all solid- state battery (ASSB).BACKGROUND[0003| All-solid-state batteries (ASSBs) are being extensively studied due to their better safety and higher energy density in comparison to liquid-electrolyte based lithium-ion batteries. ASSBs include a solid electrolyte (SE) layer between a cathode layer and an anode layer, wherein the SE layer comprises an inorganic ion conductor such as inorganic oxide or sulfide electrolyte. The SE layer functions as both electrolyte and separator. However, formation and growth of lithium dendrite may penetrate an SE layer and cause short-circuit, thus leading to a shortened life of ASSB. Thus, there remains a need for new ASSBs and methods for preparing the same.SUMMARY|0004| The present disclosure provides an all solid-state battery (ASSB) comprising an anode layer, an anode protective layer, a solid electrolyte layer, and a cathode layer in the order, wherein the anode protective layer comprises a particle of non-spherical porous carbon doped with nitrogen (nS-PNC). In some embodiments, the anode protective layer comprises a first lithiophilic material. In some embodiments, the particle of non-spherical porous carbon doped with nitrogen (nS-PNC) further comprises a second lithiophilic material. In some embodiments,the ASSB comprising the anode protective layer exhibits an improved electrochemical performance.100051 The term “particle” or “particles” herein refers to primary particle or particles unless otherwise specified. Agglomerate refers to clusters formed by the aggregation of primary particles.BRIEF DESCRIPTION OF THE FIGURES

[0006] Non-limiting embodiments of the present disclosure will be described by way of example with reference to the accompanying figures, which are schematic and are not intended to be drawn to scale. In the figures, each identical or nearly identical component illustrated is typically represented by a single numeral. For purposes of clarity, not every component is labeled in every figure, nor is every component of each embodiment of the disclosure shown where illustration is not necessary to allow those of ordinary skill in the art to understand the disclosure.

[0007] Fig. 1 illustrates a representative configuration of an ASSB with an anode protective layer according to one embodiment of the present disclosure.

[0008] Fig. 2 illustrates another representative configuration of an ASSB with an anode protective layer according to one embodiment of the present disclosure.

[0009] Fig. 3 illustrates a representative configuration of an ASSB with an anode protective layer according to one embodiment of the present disclosure.|0010] Fig. 4 shows an SEM image of particles of a non-spherical porous carbon doped with nitrogen according to one embodiment of the present disclosure.

[0011] Fig. 5 shows an SEM image of a cross-section of an anode according to another embodiment of the present disclosure.

[0012] Figs. 6A through 6F show the rate performance of cells according to some embodiments of the present disclosure.

[0013] Figs. 7A, 7B and 7C show the specific capacities, capacity retention rates and columbic efficiencies (CEs) of cells during cycling, respectively, according to some embodiments of the present disclosure.DETAILED DESCRIPTION

[0014] Disclosed is an all-solid-state battery (ASSB) comprising a cathode layer, a solid electrolyte layer, an anode protective layer and an anode layer in the order, wherein the anode protective layer comprises particles of a first lithiophilic material, a spherical carbon particle and a non-spherical porous carbon doped with nitrogen. In some embodiments, the particles of the first lithiophilic material are evenly distributed in a matrix comprising the spherical carbon particles and the non-spherical carbon particles. In some embodiments, the particle of non-spherical porous carbon doped with nitrogen (nS-PNC) further comprises a second lithiophilic material. In some embodiments, the ASSB comprising the anode protective layer exhibits a longer cycling life and an improved electrochemical performance.

[0015] In one embodiment, an ASSB comprises a cathode layer (1), an anode layer (2), a solid electrolyte (SE) layer (3), and an anode protective layer (4) between the SE layer (3) and the anode (2) as shown in Figs. 1 and 2. In some embodiments, the anode protective layer (4) comprises a first lithiophilic material that is alloyable with lithium. In some embodiments, the anode layer (2) comprises an anode current collector (2-1) and optionally an anode active material layer (2-2). In some embodiments, the cathode layer (1) comprises a cathode current collector (1-1) and a cathode active material layer (1-2).

[0016] In some embodiments, the anode layer (2) comprises an anode current collector (2-1) and an anode active material layer (2-2) prior to the first charge as shown in Fig. 1. In some embodiments, the anode layer (2) comprises an anode current collector (2-1) without an anode active material layer (2-2) prior to the first charge as shown in Fig. 2. In some embodiments, an anode active material layer (2-2) is formed after the first charge.100171 In some embodiments, the anode protective layer (4) may be a single layer or a multilayered structure. In some embodiments, the anode protective layer (4) is a single layer comprising the non-spherical porous carbon particles. As shown in Fig. 3, the anode protective layer (4) is a single layer comprising a first lithiophilic material (5), a spherical carbon particle (6), and a non-spherical porous carbon particle (7), wherein the non-spherical porous carbon particle (7) comprises a MOF-derived porous carbon framework (7-1), a non- metal dopant (7-2) and a second lithiophilic material (7-3).

[0018] In some embodiments, the content of nitrogen of a surface of the non-spherical porous carbon particles is from about 1 atomic percent to about 35 atomic percent, from about 1 atomic percent to about 30 atomic percent, from about 1 atomic percent to about 25 atomic percent, from about 1 atomic percent to about 20 atomic percent, from about 1 atomic percent to about 10 atomic percent, from about 2 atomic percent to about 35 atomic percent, from about 2 atomic percent to about 30 atomic percent, from about 2 atomic percent to about 25 atomic percent, from about 2 atomic percent to about 20 atomic percent, from about 2 atomic percent to about 10 atomic percent, about 5 atomic percent to about 35 atomic percent, from about 5 atomic percent to about 30 atomic percent, from about 5 atomic percent to about 25 atomic percent, from about 5 atomic percent to about 20 atomic percent, or from about 5 atomic percent to about 10 atomic percent, based on a total content of the surface, when determined by an SEM- energy dispersive X-ray (EDX) spectroscopy of a surface of the non-spherical porous carbon particles.

[0019] In some embodiments, the anode protective layer (4) may have two or more sublayers.

[0020] In some embodiments, the spherical carbonaceous material in the anode protective layer comprises at least one selected from the group consisting of carbon black, acetylene black, Ketjen black, channel black, furnace black, lamp black, thermal black, natural graphite and artificial graphite.

[0021] In some embodiments, the particle of the spherical carbonaceous material has a weigh percentage in a range from 30 wt% to 90 wt%, from 30 wt% to 85 wt%, from 30 wt% to 80 wt%, from 40 wt% to 90 wt%, from 40 wt% to 85 wt%, from 40 wt% to 80 wt%, from 50 wt% to 90 wt%, from 50 wt% to 85 wt%, from 50 wt% to 80 wt%, from 60 wt% to 90 wt%, from 60 wt% to 85 wt%, or from 60 wt% to 80 wt% in the anode protective layer.

[0022] In some embodiments, the first lithiophilic material in the anode protective layer comprises at least one selected from the group consisting of Ag, Zn, Ti, Cd, Mg, Al, Ga, Si, Ge, In, Sn, Pb, Bi, and Sb. In some embodiments, the first material is in the form of particles. In some embodiments, the particles of the first lithiophilic material have a median particle size (D50) in a range from 20 nm to 130 nm in the anode protective layer. In some embodiments, the first lithiophilic material has a weight percentage in a range from 5wt% to 35 wt%, from 5 wt% to 30wt%, from 5wt% to 25wt%, from 5 wt% to 20 wt%, from 10 wt% to 35 wt%, from 10 wt% to 30wt%, from 10wt% to 25wt%, from 10 wt% to 20 wt%, from 15wt% to 35 wt%, from 15 wt% to 30wt%, from 15wt% to 25wt%, or from 15 wt% to 20 wt% in the anode protective layer in the anode protective layer. In some embodiments, the first lithiophilic material has a weight percentage of no greater than 5wt% in the anode protective layer. In some embodiments the anode protective layer is substantially free of the first lithiophilic material.

[0023] In some embodiments, the non-spherical porous carbon particle is a hexahedron, octahedron, decahedron, dodecahedron, tetradecahedron, hexahedron, octahedron, or combinations thereof. In some embodiments, the non-spherical porous carbon particle is not a linear carbon material such as carbon fiber and carbon nanotube.

[0024] In some embodiments, the second lithiophilic material in non-spherical porous carbon particle comprises at least one selected from the group consisting of Ag, Zn, Ti, Cd, Mg, Al, Ga, Si, Ge, In, Sn, Pb, Bi, Sb, oxide thereof and combination thereof. In some embodiments, the second lithiophilic material is in the form of particles. In some embodiments, the second lithiophilic material is in situ formed when a non-spherical porous carbon precursor isconverted to a non-spherical porous carbon particle via a process such as carbonization. In some embodiments, the second lithiophilic material is dispersed uniformly in the non-spherical porous carbon particle. In some embodiments, the second lithiophilic material exists nanoparticles and has a median particle size (D50) in a range from 1 nm to 10 nm. In some embodiments, the second lithiophilic material is distributed within the pores of or on surface of the non-spherical porous carbon particle. In some embodiments, the second lithiophilic material serves as lithiophilic sites, improving the kinetics of lithium nucleation.

[0025] In some embodiments, the content of second lithiophilic material of a surface of the non-spherical porous carbon particles is about 0.1 atomic percent to about 10 atomic percent, based on a total content of the surface, when determined by SEM-EDX of a surface of the non- spherical porous carbon particles. In some embodiments, the non-spherical porous carbon particles are substantially free of the second lithiophilic material.

[0026] In some embodiments, the non-spherical porous carbon particles have a dominant pore size in a range from 1 nm to 8 nm. In some embodiments, the dominant pore size refers to the pore diameter corresponding to the main peak in the pore distribution plot from the isotherm desorption based on the Barrett- Joy ner-Halenda (BJH) method.

[0027] In some embodiments, the non-spherical porous carbon particles have a Brunauer- Emmett-Teller (BET) value in a range from 500 m2 / g to 2000 m2 / g.

[0028] In some embodiments, the non-spherical porous carbon particles have a median particle size (D50) in a range from about 30 nm to about 3 pm. In some embodiments, the median particle size is measured by SEM. In some embodiments, the median particle size is measured by dynamic light scattering (DLS).

[0029] In some embodiments, the non-spherical porous carbon particles have a median particle size of 664 nm ± 43 nm.

[0030] In some embodiments, at least some of the non-spherical porous carbon particles are hexahedron, octahedron, decahedron, dodecahedron, tetradecahedron, hexahedron, octahedron, or combinations thereof.

[0031] In some embodiments, the non-spherical porous carbon particles and the spherical porous carbon particles have a weight ratio of no greater than 3 / 7 or no greater than 4 / 6. In some embodiments, the non-spherical porous carbon particles and the spherical porous carbon particles have a weight ratio of no greater than 45 / 55. In some embodiments, the non-spherical porous carbon particles and the spherical porous carbon particles have a weight ratio of no greater than 2 / 8. In some embodiments, the non-spherical porous carbon particles and the spherical porous carbon particles have a weight ratio of no greater than 25 / 75. In some embodiments, the non-spherical porous carbon particles and the spherical porous carbon particles have a weight ratio of no greater than 35 / 65. .

[0032] In some embodiments, the non-spherical porous carbon particles can be prepared by carbonizing particles of metal organic frameworks (MOFs) at a temperature in a range from 500 °C to 1000 °C in a reductive gas (for example, mixture of N2 and H2) for a period. In some embodiments, ZIF-8 can be the MOFs particles. In some embodiments, Zn in the non-spherical porous carbon particles can be reduced or removed by pyrolysis at 1000 °C for more than 1 hour.

[0033] In some embodiments, the anode protective layer has a thickness in a range from 0.5 pm to 50.0 pm, from 0.5 pm to 40.0 pm, from 0.5 pm to 30.0 pm, from 0.5 pm to 20.0 pm, from 0.5 pm to 15.0 pm, from 0.5pm to 10.0 pm, from 0.5pm to 5.0 pm, from 1.0 pm to 50.0 pm, from 1.0 pm to 40.0 pm, from 1.0 pm to 30.0 pm, from 1.0 pm to 20.0 pm, from 1.0 pm to 15.0 pm, from 1.0 pm to 10.0 pm, from 1.0 pm to 5.0 pm, or any and all subranges and ranges therebetween.

[0034] In some embodiments, the carbon material, i.e., the non-spherical carbonaceous material and the spherical carbonaceous material has a volume percentage of at least 50 vol%,at least 60 vol% or at least 70 vol% in the anode protective layer so that the particles of the first lithiophilic material are distributed in a matrix of the carbon material comprising the non- spherical carbonaceous material and the spherical carbonaceous material.10035] In some embodiments, the anode protective layer comprises a first lithiophilic material, a non-spherical carbonaceous material, a spherical carbonaceous material and a polymeric binder. In some embodiments, the polymeric binder is present in a weight percentage in a range from 2 wt% to 10 wt% in the anode protective layer. In some embodiments, the polymeric binder comprises at least one selected from the group consisting of polyacrylate, styrenebutadiene rubber (SBR), polytetrafluoroethylene) (PTFE), poly(vinylidene fluoride) (PVDF), vinylidene fluoride / hexafluoropropylene copolymer, polyvinylidene fluoride-co- trichloroethylene, polyacrylonitrile, polymethylmethacrylate, polyvinylpyrrolidone, polyvinylacetate, polyethylene-co-vinyl acetate, polyethylene oxide, arylate copolymer, cellulose acetate, cellulose acetate butyrate, cellulose acetate propionate, polysaccharide polymer and carboxyl methyl cellulose, or a combination thereof.

[0036] A solid electrolyte layer (alternatively, solid electrolyte membrane or electrolyte film) refers to a thin structure that allows transportation or flow of ions and prevents electronic contact between a cathode and an anode. A solid electrolyte layer has a typical thickness in a range from 5 pm to 300 pm.

[0037] In some embodiments, the solid electrolyte is an oxide-based solid electrolyte or a sulfide-based electrolyte. In one embodiment, the solid electrolyte has a formula LixMlyM2zPi-PM3pS6-a-b-qOqClaBrb (Formula I), wherein 4<x<8, 0<y<l, 0<z <1, 0<p<l, 0<q<l, 0<a<2, 0<b<2, 0<6-a-b-q<6, 0<l-p<l, wherein Ml is at least one element of Group 1 or Group 11 other than H or Li of the periodic table, M2 is at least one element of Group 2 of the periodic table, and M3 is at least one element of Group 14 of the periodic table.

[0038] In some embodiments, the solid electrolytes has a formula LixMlyM2zPi-pM3PS6-a-b- qOqClaBrb (Formula I), wherein 4<x<8, 0<y<l, 0<z <1, 0<p<l, 0<q<l, 0<a<2, 0<b<2, 0<6-a-b-q<6, 0<l -p<l , and wherein Ml is at least one element of Group 1 or Group 11 other than H or Li of the periodic table, M2 is at least one element of Group 2 of the periodic table, and M3 is at least one element of Group 14 of the periodic table.|0039| In some embodiments, Ml is at least one selected from the group consisting of Na, K, Rb, Cs, Cu, Ag, and Au. In some embodiments, M2 is at least one selected from the group consisting of Be, Mg, Ca, Sr, and Ba. In some embodiments, M3 is at least one selected from the group consisting of Si, Ge, Sn, and Pb.

[0040] In some embodiments, b / a has a value in a range from 0 to 20, i.e, 0<b / a<20.

[0041] In some embodiments, the formula of sulfide solid electrolyte in the electrolyte layer, i.e., LixMlyM2zPi-pM3pS6-a-b-qOqClaBrb, does not comprise any of Ml, M2, M3 or O, i.e., y=z=p=q=0, corresponding to a formula of LixPSe-a-bClaBrb.

[0042] In some embodiments, the formula of the sulfide electrolyte comprises at least one element selected from the group consisting of Ml, M2, M3 and O. In some embodiments, the Formula (I) contains one element selected from the group consisting of Ml, M2, M3 and O. In some embodiments, Formula I is selected from the group consisting of:1) LixMlyPSe-a-bClaBrb, where 4<x<8, 0<y<l, 0<a<2, 0<b<2, 0<6-a-b<6;2) LixM2zPS6-a-bClaBrb, where 4<x<8, 0<z<l, 0<a<2, 0<b<2, 0<6-a-b<6;3) LixPi-pM3PS6-a-bClaBrb, where 4<x<8, 0<p<l, 0<a<2, 0<b<2, 0<6-a-b<6, 0<l-p<l; and4) LixPSe-a-b-qOqClaBrb, where 4<x<8, 0<q<l, 0<a<2, 0<b<2, 0<6-a-b-q<6.100431 In some embodiments, the Formula (I) contains O and one element selected from the group consisting of Ml, M2, and M3. In some embodiments, the sulfide solid electrolyte has a formula selected from the group consisting of LixMlyPSe-a-b-qOqClaBrb (4<x<8, 0<y< 10<q<l, 0<a<2, 0<b<2, 0<6-a-b-q<6), LixM2zPiS6-a-b-qOqClaBrb (4<x<8, 0<z<l, 0<q<l, 0<a<2, 0<b<2, 0<6-a-b-q<6,), and LixPi-pM3pS6-a-b-qOqClaBrb (4<x<8, 0<p<l, 0<q<l, 0<a<2, 0<b<2, 0<6-a-b-q<6, 0<l-p<l). In one embodiment, the Formula (I) contains O without Ml, M2, or M3. In one embodiment, the formula of the sulfide electrolyte is LixPSe-a-b-qOqClaBrb (4<x<8,0<q<l, 0<a<2, 0<b<2, 0<6-a-b-q<6). In some embodiments, Ml is at least one element of Group 1 or Group 11 other than H or Li of the periodic table. In some embodiments, Ml is at least one selected from the group consisting of Na, K, Rb, Cs, Cu, Ag, and Au. In some embodiments, M2 is at least one element of Group 2 of the periodic table. In some embodiments, M2 is at least one selected from the group consisting of Be, Mg, Ca, Sr, and Ba. In some embodiments, M3 is at least one element of Group 14 of the periodic table. In some embodiments, M3 is at least one selected from the group consisting of Si, Ge, Sn, and Pb.

[0044] In one embodiment, the sulfide solid electrolyte has a formula of LixPSe-a-b-qOqClaBrb, where 4<x<8, 0<q<l, 0<a<2, 0<b<2, 0<6-a-b-q<6. The incorporation of oxygen into the formula makes such material more stable. In some embodiments, the molar amount of O with q having a value in a range from 0 to 0.1, from 0 to 0.2, from 0 to 0.3, from 0 to 0.4, from 0 to0.5, from 0 to 0.6, from 0.001 to 0.1, from 0.001 to 0.2, from 0.001 to 0.3, from 0.001 to 0.4, from 0.001 to 0.5, from 0.001 to 0.6, from 0.002 to 0.1, from 0.002 to 0.2, from 0.002 to 0.3, from 0.002 to 0.4, from 0.002 to 0.5, from 0.002 to 0.6, from 0.005 to 0.1, from 0.005 to 0.2, from 0.005 to 0.3, from 0.005 to 0.4, from 0.005 to 0.5, from 0.005 to 0.6, or any and all ranges and subranges therebetween. In one embodiment, the formula is Li5.8PS4.70o.iCli.2.

[0045] In some embodiments, the formula is LixPSe-a-b-qOqClaBrb, wherein 4<x<8, 0<q<l, 0<a<2, 0<b<2, 0<6-a-b-q<6. In some embodiments, b / a has a value higher than zero. In some embodiments, b / a has a value in a range from 0 to 3.5. In some embodiments, b / a has a value in a range from 0 to 7. In some embodiments, b / a has a value in a range from 0 to 10, from 0 to 15, or from 0 to 20.

[0046] In some embodiments, when the formula is LixMlyPSe-a-b-qClaBrb, 4<x<8, 0<y<l, 0<a<2, 0<b<2, 0<6-a-b<6, b / a has a value in a range from 0 to 3.5. In some embodiments, b / a has a value in a range from 0 to 7. In some embodiments, b / a has a value in a range from 0 to 10, from 0 to 15, or from 0 to 20. In some embodiments, b / a has a value higher than zero.

[0047] In some embodiments, when the formula is LixM2zPS6-a-bClaBrb, where 4<x<8, 0<z<l, 0<a<2, 0<b<2, 0<6-a-b<6, b / a has a value in a range from 0 to 3.5. In some embodiments, b / a has a value in a range from 0 to 7. In some embodiments, b / a has a value in a range from 0 to 10, from 0 to 15, or from 0 to 20. In some embodiments, b / a has a value higher than zero.

[0048] In one embodiment, when the formula is LixPi-PM3PS6-a-bClaBrb, 4<x<8, 0<p<l, 0<a<2, 0<b<2, 0<6-a-b<6, 0<l-p<l, b / a has a value in a range from 0 to 3.5. In some embodiments, b / a has a value in a range from 0 to 7. In some embodiments, b / a has a value in a range from 0 to 10, from 0 to 15, or from 0 to 20. In some embodiments, b / a has a value higher than zero.

[0049] In some embodiments, the Formula (I) contains O and one element selected from the group consisting of Ml, M2, and M3. In some embodiments, the sulfide solid electrolyte has a formula selected from the group consisting of LixMlyPS6-a-b-qOqClaBrb (4<x<8, 0<y<l,0<q<l, 0<a<2, 0<b<2, 0<6-a-b-q<6), LixM2zPS6-a-b-qOqClaBrb (4<x<8, 0<z<l, 0<q<l, 0<a<2, 0<b<2, 0<6-a-b-q<6,), and LixPi-PM3PS6-a-b-qOqClaBrb (4<x<8, 0<p<l, 0<q<l, 0<a<2, 0<b<2, 0<6-a- b-q<6, 0<l-p<l). In one embodiment, the Formula (I) contains O without Ml, M2, or M3. In one embodiment, the formula of the sulfide electrolyte is LixPS6-a-b-qOqClaBrb (4<x<8, 0<q<l, 0«2. 0<b<2, 0<6-a-b-q<6). In some embodiments, the molar amount of Br in the formula has a value higher than zero, i.e., b>0.

[0050] In some embodiments, the total molar amount of the halogen in the formula of sulfide electrolyte is no more than 2, i.e., a+b<2. In one embodiment, the total molar amount of the halogen in the formula is no less than 2 and no more than 3, i.e., 2<a+b<3. In one embodiment, the total molar amount of the halogen in the formula is no less than 2 and less than 4, i.e., 2<a+b<4. In one embodiment, the total molar amount of Br and Cl in the formula is no more than 2, i.e., a+b<2, no less than 2 and no more than 3, i.e., 2<a+b<3, or no less than 2 and less than 4, i.e., 2<a+b<4.

[0051] In some embodiments, the sulfide solid electrolyte has a formula selected from the group consisting of:1) LixPSe-a-bClaBrb, where 4<x<8, 0<a<2, 0<b<2, 0<6-a-b<6;2) LixMlyPSe-a-bClaBrb, where 4<x<8, 0<y<l, 0<a<2, 0<b<2, 0<6-a-b<6;3) LixM2zPS6-a-bClaBrb, where 4<x<8, 0<z<l, 0<a<2, 0<b<2, 0<6-a-b<6;4) LixPi-pM3pS6-a-bClaBrb, where 4<x<8, 0<p<l, 0<a<2, 0<b<2, 0<6-a-b<6, 0<l-p<l;5) LixPSe-a-b-qOqClaBrb, where 4<x<8, 0<q<l, 0<a<2, 0<b<2, 0<6-a-b-q<6;6) LixMlyPSe-a-b-qOqClaBrb, where 4<x<8, 0<y<l,0<q<l, 0<a<2, 0<b<2, 0<6-a-b-q<6;7) LixM2zPS6-a-b-qOqClaBrb, where 4<x<8, 0<z<l, 0<q<l, 0<a<2, 0<b<2, 0<6-a-b-q<6;8) LixPi-pM3pS6-a-b-qOqClaBrb, where 4<x<8, 0<p<l, 0<q<l, 0<a<2, 0<b<2, 0<6-a-b-q<6, 0<l-p<l; and mixtures thereof.

[0052] In some embodiments, the solid electrolyte layer has a thickness in a range from 5 pm to 300 pm, from 10 pm to 300 pm, from 20 pm to 300 pm, from 50 pm to 300 pm, from 5 pm to 200 pm, from 10 pm to 200 pm, from 20 pm to 200 pm, from 50 pm to 200 pm, from 5 pm to 100 pm, from 10 pm to 100 pm, from 20 pm to 100 pm, from 50 pm to 100 pm, from 5 pm to 50 pm, from 10 pm to 50 pm, from 20 pm to 50 pm, or any and all ranges and subranges therebetween.

[0053] In some embodiments, the solid electrolyte layer has a lithium-ion conductivity of no less than 0.05 mS / cm, no less than 0.1 mS / cm, no less than 0.2 mS / cm, no less than 0.5 mS / cm, no less than 0.75 mS / cm, no less than 1 mS / cm, no less than 2 mS / cm, or no less than 5 mS / cm, no less than 7.5 mS / cm or no less than 10 mS / cm. In some embodiments, the solid electrolyte layer has a lithium-ion conductivity in a range from 0.05 mS / cm to 10 mS / cm, from 0.1 mS / cm to 10 mS / cm, from 0.25 mS / cm to 10 mS / cm, from 0.5 mS / cm to 10 mS / cm, from 0.75 mS / cm to 10 mS / cm, from 1 mS / cm to 10 mS / cm, from 2 mS / cm to 10 mS / cm, from 0.05 mS / cm to 7.5 mS / cm, from 0.1 mS / cm to 7.5 mS / cm, from 0.25 mS / cm to 7.5 mS / cm, from 0.5 mS / cm to 7.5 mS / cm, from 0.75 mS / cm to 7.5 mS / cm, from 1 mS / cm to 7.5 mS / cm, from 2 mS / cm to7.5 mS / cm, from 0.05 mS / cm to 5 mS / cm, from 0.1 mS / cm to 5 mS / cm, from 0.25 mS / cm to5 mS / cm, from 0.5 mS / cm to 5 mS / cm, from 0.75 mS / cm to 5 mS / cm, from 1 mS / cm to 5 mS / cm, or any and all ranges and subranges therebetween.|0054| In one embodiment, the cathode active material layer of an ASSB comprises a cathode active material. In some embodiments, the ASSB has a relatively high cathode loading. In some embodiments, the ASSB has a cathode loading of at least 5.0 mAh / cm2, at least 5.5 mAh / cm2, at least 6.0 mAh / cm2, at least 6.5 mAh / cm2, at least 6.8 mAh / cm2, at least 7.2 mAh / cm2, or at least 7.5 mAh / cm2. A high cathode loading is critical to achieve a high energy density. However, a battery with a high cathode loading may be subject to a relatively fast decay, which ultimately leads to a lower capacity retention. In some embodiments, the present disclosure provides an ASSB having both a high cathode loading and a good cycling performance.(0055] In some embodiments, the ASSB exhibits an initial specific capacity of at least 200 mAh / g at a rate of 0.1C at a temperature of 45 °C. In some embodiments, the ASSB exhibits an initial specific capacity of at least 165 mAh / g at a rate of 0.33C at a temperature of 45 °C. In some embodiments, the ASSB is tested at a pressure in a range from 0.5 MPa to 5.0 MPa.

[0056] In some embodiments, the cycling test can be performed at other C rates such as C / 6, C / 4, C / 2, C, 1C, 2C, 3C, 5C, or any intermediate rate therebetween. In some embodiments, the cycling test can be performed at other temperatures such as -20°C, -10°C, 0°C, 10°C, 20°C 25°C, 30 °C, 40°C, 50°C, 80 °C, or any intermediate temperature therebetween. Cycle life is determined by the number of cycles for the battery cell to reach a threshold value such as 80% of its original capacity and is usually used to measure the cycling performance of a secondary battery. In some embodiments, the ASSB comprising the anode protective layer exhibits a cycle life which is at least 10%, at least 15%, at least 20%, at least 25%, at least 30%, at least 40%, at least 50%, or at least 60% longer than that of the ones without such non-spherical porous carbon material.(0057] In some embodiments, the ASSB exhibits a capacity retention rate of at least 94.00%, at least 95.00%, at least 96.00%, at least 97.00%, at least 98.00%, at least 98.50%, at least99.00%, at least 99.50%, at least 99.75% or at least 99.90% after at least 70 cycles at a rate of0.33C / 0.33C at 45 °C.

[0058] In some embodiments, after 70 cycles at a rate of 0.33C / 0.33C at a temperature of 45 °C, the AS SB exhibits a specific capacity of at least 160 mAh / g, at least 163 mAh / g, at least 165 mAh / g, at least 168 mAh / g, or at least 170 mAh / g.

[0059] In some embodiments, the AS SB exhibits an average CE of an average CE of at least 99.75%, at least 99.77%, at least 99.80%, or at least 99.82% for the first 70 cycles at a rate of 0.33C / 0.33C at a temperature of 45 °C,

[0060] In one embodiment, the cathode active material layer in the cathode layer of an ASSB comprises a cathode electroactive material. In one embodiment, the cathode active material contains Li, Ni, and Co. In one embodiment, the cathode active material contains Li, Ni, and Co and at least one of Mn and Al. In one embodiment, the cathode active material contains at least one of Fe, and P.

[0061] In one embodiment, the cathode active material experiences a redox reaction at a potential of 2 V or above over Li / Li+during operation of an ASSB.

[0062] In some embodiments, the anode active material layer comprises an anode active material such as lithium metal or a lithium alloy. In some embodiments, the anode active material comprises at least one selected from the group consisting of lithium, sodium, magnesium, aluminum, silicon, calcium, titanium, manganese, iron, cobalt, nickel, zinc, molybdenum, silver, indium, tin, and tungsten. In some embodiments, the anode active material layer also includes a carbon-based conductive material with a weight percentage in a range from 1 wt% to 30 wt%. In some embodiments, the carbon-based conductive material in the anode active material layer comprises at least one selected from the group consisting of carbon black, acetylene black, Ketjen black, channel black, furnace black, lamp black, thermal black, natural graphite and artificial graphite.

[0063] In one aspect, the present disclosure provides a method for preparing an anode protective layer. The method comprises:1) Preparing a mixture comprising particles of a first lithiophilic material, spherical carbonaceous particles, particles of a non-spherical porous carbon, and a solvent; and2) Coating the mixture to a substrate followed by drying, thus obtaining an anode protective layer.

[0064] In some embodiments, the spherical carbonaceous particles are carbon black. In some embodiments, the substrate is an anode current collector or a detachable base such as peelable film.

[0065] In some embodiments, the anode current collector is an SUS (stainless steel) foil.

[0066] In some embodiments, the mixture further comprises a polymer binder including without limitation polyvinylidene fluoride (PVDF).

[0067] In some embodiments, the solvents comprise at least one selected from the group consisting of N-methylpyrrolidone (NMP), 1,3-dioxolane, 2,5,7, 10-tetraoxaundecane, and mixtures thereof.

[0068] In some embodiments, the solvent has a weight percentage ranging from 25% to 75% in the slurry.

[0069] In some embodiments, the present disclosure provides a method for preparing an all- solid-state battery (ASSB), the method comprising:1) having an anode layer comprising an anode current collector and an anode protective layer, wherein the anode protective layer comprises a non-spherical porous carbon particle, and2) laminating the anode layer with the anode protective layer, a solid electrolyte layer, and a cathode layer in the order, thereby obtaining an ASSB comprising the anode layer, the solid electrolyte layer and the cathode layer wherein the anode protective layer comprising the non-spherical porous carbon particle.

[0070] In some embodiments, the anode layer, the solid electrolyte layer and the cathode layer are laminated via an isostatic pressing (IP) process.

[0071] In some embodiments wherein the IP process is conducted at a stacking pressure in a range from 100 MPa to 500 MPa.

[0072] In some embodiments, the IP process is conducted at a temperature in a range from 20 °C to 100 °C.

[0073] In some embodiments, the anode protective layer is a structure with a gradient concentration, wherein the anode protective layer contains particles of a non-spherical particle of a porous carbonaceous material with a decreasing or increasing concentration gradient along a first direction along the thickness direction, wherein the first direction is defined as the direction the SE layer faces toward an anode.

[0074] In some embodiments, the anode layer, the anode protective layer, the solid electrolyte layer and the cathode layer are laminated or assembled under an isostatic pressing (IP) process. In some embodiments, the IP is conducted under a pressure in a range from 100 MPa to 500 MPa. In some embodiments, the IP is performed at a temperature in a range from 20 °C to 100 °C.

[0075] The disclosure will be better understood by reference to the Experimental Details which follow, but those skilled in the art will readily appreciate that the specific experiments detailed are only illustrative, and are not meant to limit the disclosure as described herein, as numerous variations and modifications of these exemplary embodiments are possible without undue experimentation. All such variations and modifications are within the scope of the teachings of this disclosure. It will be appreciated that the foregoing description and following examples, no matter how detailed they may appear in text, the disclosure may be practiced in many ways, and the disclosure should be construed in accordance with the appended claims and equivalents thereof.EXAMPLESPreparation of non-spherical porous carbon particles

[0076] ZIF-8, a zeolitic imidazolate frameworks (ZIF) which is a subclass of metal organic frameworks (MOFs), was selected as the carbon precursors in this example. ZIF-8 is composed of a zinc center coordinated by four imidazolate groups. Typically, a first solution was prepared by dissolving 1.78 g Zn(NOs)2 6H2O in a mixed solvent of 40 mL ethanol and 40 mL methanol. A second solution was prepared by dissolving 2.95g 2-methylimidazole with 40 mL methanol and 40 mL ethanol. The second solution was then added into the first solution under magnetic stirring to obtain a mixture, which was left standing still for 48 h at room temperature to form precipitate. ZIF-8 particles were obtained by collecting the precipitate followed by washing with methanol and drying in an oven at 60 °C. The as-synthesized ZIF-8 particles were transferred into a flow furnace and heated to 800 °C for 2 h in a flowing gas (3% H2 + 97% N2). Non-spherical particles of porous carbon material were collected after the furnace was turned off and cooled down.SEM and Elemental analysis

[0077] Scanning electron microscopy (SEM) images and energy-dispersive X-ray (EDX) analysis were taken on a Thermo Scientific electron microscopy at 10.0 kV and 65 pA.

[0078] Fig. 4 shows an SEM image of the non-spherical particles of the porous carbonaceous material. It clearly shows the non-spherical morphology of the porous carbon material. An image analysis showed that the median particle size of these non-spherical particles is 664 nm ± 43 nm.

[0079] Table 1 shows the elemental composition of the as synthesized non-spherical porous carbon particles based on EDX analysis. It suggests that the content of nitrogen of a surface of the non-spherical porous carbon particles is about 16.3 atomic percent based on a total content of the surface, when determined by SEM-EDX. It also suggests that the content of zinc (Zn) (a second lithiophilic material) of a surface of the non-spherical porous carbon particles is about 6.1 atomic percent based on a total content of the surface, when determined by SEM-EDX.Table 1 Elemental composition of non-spherical porous carbon particles according to some embodiments of the present disclosurePreparation of anode protective layer and assembly of AS SB

[0080] Ag particles with a median particle size (D50) around 20-130 nm were mixed with carbon black (CB) as the spherical carbon particles, the non-spherical particles of porous carbon material as synthesized, polyvinylidene fluoride (PVDF) as binder and N- methylpyrrolidone (NMP) as solvent, resulting in a slurry. The slurry was coated on an SUS (stainless steel) foil with a thickness of 10 pm as anode current collector using a bar-coating method followed by drying in a convection oven. The thickness of the anode protective layer on the anode current collector was 15 ~20 pm.Table 2 Composition of the anode protective layer and resistance of cell according to some embodiments of the present disclosure

[0081] The compositions of the anode protective layers of examples 1 through 5 (Ex. 1, Ex. 2,Ex. 3, Ex. 4 and Ex. 5) are summarized in Table 2. An anode protective layer of comparative example 1 was also prepared in the same manner except that CB was the only carbonaceous material, i.e., no non-spherical porous carbon particles.

[0082] A cell comprising a cathode (85wt% CAM) with a cathode loading of around 6.8mAh / cm2, an anode as prepared above, and an SE layer was assembled and sealed in a pouch followed by an isostatic pressing, leading to a pouch cell.Assembly of cells and testing

[0083] Cells comprising a cathode layer, an anode layer with an anode protective layer and a solid electrolyte layer were assembled and sealed in a pouch followed by an isostatic pressing (IP).

[0084] Fig. 5 shows an SEM image of a cross-section of Example 2 (Ex. 2), wherein the anode protective layer (4) is adjacent to the anode current collector (2-1) and comprises non-spherical particles of porous carbon material (7).]0085[ Rate testing of the cells was conducted under the same conditions with the charge rate at 0.1C and the discharge rate changing from 0.1C to 0.33C, 1C and then back to 0.1C sequentially.

[0086] The rate performance of comparative example 1 and examples 1 through 5 are shown in Figs. 6A through 6F and Table 3.

[0087] Examples 1 through 3 exhibited a higher or comparable discharge capacity (DChg Cap.) than the comparative example 1 at higher C rates (0.33C and 1C) while Examples 4 and 5 exhibited a much worse rate performance. It clearly shows that the weight ratio of spherical carbon particles to the non-spherical particles plays a critical role in influencing the rate performance.

[0088] Without wishing to be bound by any theory, the second lithiophilic material, Zn in this example, in the non-spherical particles and / or the particular morphology of the particle regulate the nucleation kinetics of lithium and thus improves the rate performance. However, when the content of the non-spherical particle is too high, the anode protective layer may have a less- stacked structure, leading to a higher resistance as shown in Table 2 and relatively poor capability in controlling the ionic transportation and lithium nucleation.Table 3 Rate performance of examples and comparative examples(0089] Cycling testing of the cells was conducted under 0.33C / 0.33C continuously at 45 °C with an external pressure in a range from 0.5MPa to 5.0MPa, wherein each cycle charges to 4.25 V and discharges to 2.5V.

[0090] Specific capacity, capacity retention rate and columbic efficiency (CE) during first 100 cycles are shown in Figs. 7A, 7B and 7C, respectively.

[0091] As shown in Table 4, the cell comprising comparative example 1 (Comp. Ex. 1), example 1 (Ex. 1), example 2 (Ex. 2), example 3 (Ex. 3), example 4 (Ex. 4) and example 5 (Ex.5) exhibited a 1stdischarge specific capacity of 168.88 mAh / g, 166.20 mAh / g, 171.59 mAh / g, 165.62 mAh / g, 149.16 mAh / g, and 122.74 mAh / g at 0.33C, respectively.

[0092] Examples 4 and 5 exhibited a discharge capacity much lower than the other examples. It may be ascribed to the increased resistance and poor stacking of the anode protective layer due to incorporation of an excessive amount of a carbon particle with non-regular morphology. It also supports that the content of the non-spherical particle plays an important role in regulating the discharge capacity. As shown in Figs. 7A and 7B, the cell with example 5 exhibited a poor cycling performance and the cycling test was terminated after 6 cycles.Table 4 Cycling performance of examples and comparative examples

[0093] After 70 cycles at 45 °C and at 0.33C, the cell with Ex. 1, Ex. 2 and Ex. 3 as anode protective layer exhibited a capacity retention rate of 101.04%, 97.81% and 101.97%, respectively. Each is higher than that of the cell with comparative example 1 as anode protective layer with a capacity retention of 92.88%. When the weight ratio of the non- spherical carbon particles to the spherical carbon particles is 4 / 6 (Ex. 4), the discharge capacity is significantly lower than the comparative example 1 and examples 1 through 3. When the weight ratio of the non-spherical carbon particles to the spherical carbon particles is 5 / 5 (Ex. 5), the cell degraded quickly to a retention rate of lower than 80% after only 6 cycles.(0094] The average CE of the first 70 cycles of the cell with Ex. 1, Ex. 2 and Ex. 3 as anode protection layer is 99.79%, 99.80% and 99.86%, respectively. It is higher than comparative example 1 which has an average CE of 99.73%.

[0095] The result suggests that anode protective layer as disclosed herein with an appropriate content of the non-spherical porous carbon particle can improve the capacity retention rate during cycling and elongate the cycle life.Aspects

[0096] In a first aspect, the present disclosure provides an anode protective layer for an all- solid-state battery (ASSB). The anode protective layer comprises particles of a first lithiophilic material, spherical carbon particles and non-spherical porous carbon particles doped with nitrogen. In some embodiments, the particles of the first lithiophilic material are evenly distributed in a matrix comprising the spherical carbon particles and the non-spherical carbon particles.

[0097] In a second aspect according to the first aspect, the content of nitrogen of a surface of the non-spherical porous carbon particles is about 5 atomic percent to about 25 atomic percent, based on a total content of the surface, when determined by SEM-EDX of a surface of the non- spherical porous carbon particles.(0098] In a third aspect according to the first aspect, the non-spherical porous carbon particles have a dominant pore size in a range from 1 nm to 8 nm.

[0099] In a fourth aspect according to the first aspect, the non-spherical porous carbon particles have a Brunauer-Emmett-Teller (BET) surface area in a range from 500 m2 / g to 2000 m2 / g.

[0100] In a fifth aspect according to the first aspect, at least some of the non-spherical porous carbon particles are hexahedron, octahedron, decahedron, dodecahedron, tetradecahedron, hexahedron, octahedron, or combinations thereof.

[0101] In a sixth aspect according to the first aspect, the non-spherical porous carbon particles have a median particle size (D50) in a range from about 30 nm to about 5 pm.[0102 j In a seventh aspect according to the first aspect, the non-spherical carbon particles and the spherical porous carbon particles have a weight ratio of no greater than 3 / 7.

[0103] In an eighth aspect according to the first aspect the first lithiophilic material has a weight percentage in a range from 10 wt% to 35 wt% in the anode protective layer. In some embodiments, the first lithiophilic material comprises at least one selected from the group consisting of Ag, Zn, Ti, Cd, Mg, Al, Ga, Si, Ge, In, Sn, Pb, Bi, and Sb. In some embodiments, the anode protective layer comprises a polymeric binder with a weight percentage in a rangefrom 2 wt% to 10 wt%. In some embodiments, the polymeric binder comprises at least one selected from the group consisting of polyacrylate, styrene-butadiene rubber (SBR), polytetrafluoroethylene (PTFE), poly(vinylidene fluoride) (PVDF), vinylidene fluoride / hexafluoropropylene copolymer, polyvinylidene fluoride-co-trichloroethylene, polyacrylonitrile, polymethylmethacrylate, polyvinylpyrrolidone, polyvinylacetate, polyethylene-co-vinyl acetate, polyethylene oxide, arylate copolymer, cellulose acetate, cellulose acetate butyrate, cellulose acetate propionate, polysaccharide polymer and carboxyl methyl cellulose, or a combination thereof.

[0104] In a nineth aspect according to the first aspect, the non-spherical porous carbon particles further comprise a second lithiophilic material, wherein the second lithiophilic material is located within pores or on surface of the non-spherical porous carbon particles. In some embodiments, the second lithiophilic material comprises at least one elementary substance selected from the group consisting of Ag, Zn, Ti, Cd, Mg, Al, Ga, Si, Ge, In, Sn, Pb, Bi, Sb, one or more of oxides, sulfides, fluorides, nitrides, chlorides, and carbides thereof, and mixtures thereof.

[0105] In a tenth aspect according to the nineth aspect, the content of second lithiophilic material of a surface of the non-spherical porous carbon particles is about 0.1 atomic percent to about 10 atomic percent, based on a total content of the surface, when determined by SEM- EDX of the surface of the non-spherical porous carbon particles.|0106| In an eleventh aspect according to the first aspect, the spherical carbon particles comprise at least one selected from the group consisting of carbon black, acetylene black, Ketjen black, channel black, furnace black, lamp black, thermal black, natural graphite and artificial graphite and the spherical carbon particles have a weight percentage in a range from 30 wt% to 90 wt% in the anode protective layer.

[0107] In a twelfth aspect, the present disclosure provides an anode assembly comprising the anode protective layer of any preceding aspect and an anode current collector.101.081 In a thirteenth aspect according to the twelfth aspect, the anode assembly does not have any anode active material layer, wherein the anode protective layer is on one side of the anode current collector.[01091 In a fourteenth aspect according to the twelfth aspect, the anode assembly further comprises an anode active material layer, wherein the anode active material layer is disposed between the anode current collector and the anode protective layer. In some embodiments, the anode active material layer comprises lithium metal or lithium alloy as an anode active material.

[0110] In a fifteenth aspect, the present disclosure provides an electrochemical device comprising the anode assembly according to the twelfth aspect.

[0111] In some embodiments, the electrochemical device exhibits at least one of the following: a) an initial specific capacity of at least 165 mAh / g at a rate of 0.33C at a temperature of 45 °C, b) a capacity retention of at least 92.5 % after 70 cycles at a rate of 0.33C at a temperature of 45 °C, c) a specific capacity of at least 156 mAh / g after 70 cycles at a rate of 0.33C at a temperature of 45 °C, and d) an average CE of at least 99.75 % for the first 70 cycles at a rate of 0.33C at a temperature of 45 °C.10.112] In some embodiments, the present disclosure provides a method for preparing an ASSB, comprising:1) having an anode layer comprising an anode current collector and an anode protective layer, wherein the anode protective layer comprises particles of a first lithiophilic material, spherical carbon particles and non-spherical porous carbon particles doped with nitrogen, and2) laminating the anode layer with the anode protective layer, a solid electrolyte layer, and a cathode layer in the order, wherein the anode protective layer faces toward thesolid electrolyte layer, thereby obtaining an ASSB comprising the anode layer, the solid electrolyte layer and the cathode layer.

[0113] In some embodiments, the anode layer, the solid electrolyte layer and the cathode layer are laminated via an isostatic pressing (IP) process. In some embodiments, the IP process is conducted at a stacking pressure in a range from 100 MPa to 500 MPa at a temperature in a range from 20 °C to 100 °C.

[0114] All transitional phrases such as “comprising,” “including,” “carrying,” “having,” “containing,” “involving,” “holding,” “composed of,” and the like are to be understood to be open-ended, i.e., to mean including but not limited to. Only the transitional phrases “consisting of’ and “consisting essentially of’ shall be closed or semi-closed transitional phrases, respectively.

[0115] Certain features that are described in this specification in the context of separate embodiments can also be implemented in combination in a single embodiment. Conversely, various features that are described in the context of a single embodiment can also be implemented in multiple embodiments separately or in any suitable subcombination. Moreover, although features may be described above as acting in certain combinations and even initially claimed as such, one or more features from a claimed combination can in some cases be excised from the combination, and the claimed combination may be directed to a subcombination or variation of a subcombination.

[0116] Various embodiments of the features of this disclosure are described herein. However, it should be understood that such embodiments are provided merely by way of example, and numerous variations, changes, and substitutions can occur to those skilled in the art without departing from the scope of this disclosure. It should also be understood that various alternative to the specific embodiments described herein are also within the scope of this disclosure.

Claims

What is claimed is:

1. An anode protective layer for an all-solid-state battery (ASSB), comprising particles of a first lithiophilic material, spherical carbon particles and non-spherical porous carbon particles doped with nitrogen.

2. The anode protective layer of claim 1, wherein the content of nitrogen of a surface of the non-spherical porous carbon particles is about 5 atomic percent to about 25 atomic percent, based on a total content of the surface, when determined by SEM-EDX of the surface of the non-spherical porous carbon particles.

3. The anode protective layer of claim 1, wherein the non-spherical porous carbon particles have a dominant pore size in a range from 1 nm to 8 nm.

4. The anode protective layer of claim 1, wherein at least some of the non-spherical porous carbon particles are hexahedron, octahedron, decahedron, dodecahedron, tetradecahedron, hexahedron, octahedron, or combinations thereof.

5. The anode protective layer of claim 1, wherein the non-spherical porous carbon particles have a Brunauer-Emmett-Teller (BET) surface area in a range from 500 m2 / g to 2000 m2 / g.

6. The anode protective layer of claim 1, wherein the non-spherical porous carbon particles have a median particle size (D50) in a range from about 30 nm to about 5 pm.

7. The anode protective layer of claim 1, wherein the non-spherical carbon particles and the spherical porous carbon particles have a weight ratio of no greater than 3 / 7.

8. The anode protective layer of claim 1, wherein the first lithiophilic material has a weight percentage in a range from 10 wt% to 35 wt% in the anode protective layer.

9. The anode protective layer of claim 1, wherein the non-spherical porous carbon particles further comprise a second lithiophilic material, wherein the second lithiophilic material is located within pores or on surface of the non-spherical porous carbon particles.

10. The anode protective layer of claim 9, wherein the content of second lithiophilic material of a surface of the non-spherical porous carbon particles is about 0.1 atomic percent to about 10 atomic percent, based on a total content of the surface, when determined by SEM- EDX of the surface of the non-spherical porous carbon particles.

11. The anode protective layer of claim 1, wherein the spherical carbon particles comprise at least one selected from the group consisting of carbon black, acetylene black, Ketjen black, channel black, furnace black, lamp black, thermal black, natural graphite and artificial graphite and wherein the spherical carbon particles have a weight percentage in a range from 30 wt% to 90 wt% in the anode protective layer.

12. An anode assembly comprising the anode protective layer of any preceding claim and an anode current collector.

13. The anode assembly of claim 12, wherein the anode assembly does not have any anode active material layer, wherein the anode protective layer is on one side of the anode current collector.

14. The anode assembly of claim 12, further comprising an anode active material layer, wherein the anode active material layer is disposed between the anode protective layer and the anode active material layer.

15. An electrochemical device comprising the anode assembly of claim 12.

Images