All-solid secondary battery and method of preparing the same
An all-solid secondary battery includes a cathode layer including a cathode active material layer; an anode layer; and a solid electrolyte layer disposed between the cathode layer and the anode layer, wherein the anode layer includes an anode current collector and a first anode active material layer is disposed on the anode current collector, wherein the first anode active material layer includes an organic electrolyte and an anode active material that is capable of forming an alloy with lithium or a compound with lithium, and wherein the organic electrolyte includes an organic salt including an organic cation and an anion.
1. An all-solid secondary battery comprising:
a cathode layer comprising a cathode active material layer;
an anode layer; and
a solid electrolyte layer disposed between the cathode layer and the anode layer,
wherein the anode layer comprises an anode current collector and a first anode active material layer disposed on the anode current collector,
wherein the first anode active material layer comprises an organic electrolyte and an anode active material that is capable of forming an alloy with lithium or a compound with lithium,
wherein the anode active material comprises at least one of a carbon-containing anode active material, a metal anode active material, or metalloid anode active material,
wherein the first anode active material layer comprises the organic electrolyte in a range from about 0.1 parts by weight to about 2.5 parts by weight, based on 100 parts by weight of the anode active material,
wherein the organic electrolyte comprises an organic salt comprising an organic cation and an anion, and
wherein the organic cation comprises a heterocyclic cation comprising 1 to 3 heteroatoms.
2. The all-solid secondary battery of claim 1 , wherein the organic salt comprises a compound represented by Formula 2:
wherein, in Formula 2,
is a heterocycloalkyl or heteroaryl ring comprising 1 to 3 heteroatoms and 2 to 30 carbon atoms, wherein the ring is unsubstituted or substituted with a substituent group,
X 2 is —N(R 5 )(R 6 )—, —N(R 5 )═, —P(R 5 )═, or —P(R 5 )(R 6 )—,
the substituent group substituted in the ring, R 5 , and R 6 are each independently hydrogen, an unsubstituted or halogen-substituted C1-C30 alkyl group, an unsubstituted or halogen-substituted C1-C30 alkoxy group, an unsubstituted or halogen-substituted C6-C30 aryl group, an unsubstituted or halogen-substituted C6-C30 aryloxy group, an unsubstituted or halogen-substituted C3-C30 heteroaryl group, an unsubstituted or halogen-substituted C3-C30 heteroaryloxy group, an unsubstituted or halogen-substituted C4-C30 cycloalkyl group, or an unsubstituted or halogen-substituted C3-C30 heterocycloalkyl group, and
Y − is an anion.
3. The all-solid secondary battery of claim 1 , wherein the organic salt comprises a compound represented by at least one of Formula 4:
wherein, in Formula 4,
Z is N or P,
R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , and R 17 are each independently hydrogen, an unsubstituted or halogen-substituted C1-C30 alkyl group, an unsubstituted or halogen-substituted C6-C30 aryl group, an unsubstituted or halogen-substituted C3-C30 heteroaryl group, an unsubstituted or halogen-substituted C4-C30 cycloalkyl group, or an unsubstituted or halogen-substituted C3-C30 heterocycloalkyl group, and
Y − is an anion.
4. The all-solid secondary battery of claim 1 , wherein the organic salt comprises a compound represented by at least one of Formulae 6 to 10:
wherein, in Formulae 6 to 10,
R 22 , R 23 , R 24 , R 25 , R 26 , R 27 , and R 28 are each independently hydrogen, an unsubstituted or halogen-substituted C1-C30 alkyl group, an unsubstituted or halogen-substituted C6-C30 aryl group, an unsubstituted or halogen-substituted C3-C30 heteroaryl group, an unsubstituted or halogen-substituted C4-C30 cycloalkyl group, or an unsubstituted or halogen-substituted C3-C30 heterocycloalkyl group, and
Y − is an anion.
5. The all-solid secondary battery of claim 1 , wherein the organic salt comprises:
at least one of a pyrrolidinium cation, a pyridinium cation, a pyrimidinium cation, an imidazolium cation, a piperidinium cation, a pyrazolium cation, an oxazolium cation, a pyridazinium cation, or a triazolium cation; and
at least one anion.
6. The all-solid secondary battery of claim 1 , wherein the organic salt comprises a polymer represented by Formula 11:
wherein, in Formula 11,
is a heterocycloalkyl or heteroaryl ring comprising 1 to 3 heteroatoms and 2 to 30 carbon atoms, wherein the ring is unsubstituted or substituted with a substituent group,
X is —N(R 5 )(R 6 )—, —N(R 5 )═, —P(R 5 )═, or—P(R 5 )(R 6 )—,
R 1 to R 6 are each independently an unsubstituted or halogen-substituted C1-C30 alkyl group, an unsubstituted or halogen-substituted C6-C30 aryl group, an unsubstituted or halogen-substituted C3-C30 heteroaryl group, an unsubstituted or halogen-substituted C4-C30 cycloalkyl group, or an unsubstituted or halogen-substituted C3-C30 heterocycloalkyl group,
Y − is an anion,
a and b are each independently an integer from 1 to 5, and
n is an integer from 2 to 2800.
7. The all-solid secondary battery of claim 1 , wherein the anion comprises at least one of BF 4 − , PF 6 − , AsF 6 − , SbF 6 − , AlCl 4 − , HSO 4 − , ClO 4 − , CH 3 SO 3 , CF 3 CO 2 − , Cl − , Br − , I − , BF 4 − , SO 4 − , bis(oxalate) borate, CF 3 SO 3 , CF 3 CO 2 , (C 2 F 5 SO 2 ) 2 N, (C 2 F 5 SO 2 ) (CF 3 SO 2 )N − , or (CF 3 SO 2 ) 2 N − .
8. The all-solid secondary battery of claim 1 , wherein the organic electrolyte further comprises a lithium salt,
wherein the lithium salt comprises at least one of LiPF 6 − , LiBF 4 − , LiCF 3 SO 3 , Li(CF 3 SO 2 ) 2 N, LiC 2 F 5 SO 3 , Li(FSO 2 ) 2 N, LiC 4 F 9 SO 3 , LiN(SO 2 CF 2 CF 3 ) 2 , or compounds represented by Formulae 11 to 14,
9. The all-solid secondary battery of claim 7 , wherein a concentration of a lithium salt in the organic electrolyte is in a range from about 0.01 moles per liter to about 5 moles per liter.
10. The all-solid secondary battery of claim 1 ,
wherein the metal anode active material or metalloid anode active material has a lithium ion diffusion coefficient higher than that of lithium metal.
11. The all-solid secondary battery of claim 1 , wherein the metal or metalloid anode active material comprises at least one of indium, silicon, gallium, tin, aluminum, titanium, zirconium, niobium, germanium, antimony, bismuth, gold, platinum, palladium, magnesium, silver, or zinc.
12. The all-solid secondary battery of claim 1 , wherein the carbon-containing anode active material comprises amorphous carbon.
13. The all-solid secondary battery of claim 1 , wherein the anode active material comprises a mixture of a first particle comprising amorphous carbon and a second particle comprising a metal or a metalloid,
wherein an amount of the second particles is in a range from about 1 weight percent to about 60 weight percent based on the total weight of the mixture.
14. The all-solid secondary battery of claim 1 , wherein the first anode active material layer further comprises a binder, wherein an amount of the organic electrolyte is in a range of about 1 part by weight to about 50 parts by weight based on 100 parts by weight of the binder.
15. The all-solid secondary battery of claim 1 , wherein a thickness of the first anode active material layer is in a range from about 1 micrometer to about 50 micrometer,
wherein an interfacial resistance of the all-solid secondary battery comprising the first anode active material layer obtained by impedance measurement at a temperature of 25° C. is about 70 ohm square centimeter or less.
16. The all-solid secondary battery of claim 1 , further comprising a second anode active material layer disposed between the anode current collector and the first anode active material layer or between the solid electrolyte layer and the first anode active material layer,
wherein the second anode active material layer is a metal layer comprising lithium or a lithium alloy.
17. The all-solid secondary battery of claim 1 , wherein the solid electrolyte layer comprises at least one of a sulfide-containing solid electrolyte or an oxide-containing solid electrolyte,
wherein the oxide-containing solid electrolyte comprises at least one of L i1+x+y Al x Ti 2-x Si y P 3-y O 12 , wherein 0<x<2 and 0≤y<3, BaTiO 3 , Pb(Zr a Ti 1-a )O 3 , wherein 0≤a≤1, Pb 1-x La x Zr 1-y Ti y O 3 , wherein 0≤x<1 and 0≤y<1, PB(Mg 1/3 Nb 2/3 )O 3 —PbTiO 3 , HfO 2 , SrTiO 3 , SnO 2 , CeO 2 , Na 2 O, MgO, NiO, CaO, BaO, ZnO, ZrO 2 , Y 2 O 3 , Al 2 O 3 , TiO 2 , SiO 2 , Li 3 PO 4 − , Li x Ti y (PO 4 ) 3 , wherein 0<x<2 and 0<y<3, Li x Al y Ti z (PO 4 ) 3 , wherein 0<x<2, 0<y<1, and 0<z<3, Li 1+x+y (Al a Ga 1-a ) x (Ti b Ge 1-b ) 2-x Si y P 3-y O 12 , wherein 0≤x≤1, 0≤y≤1, 0≤a≤1, and 0≤b≤1, Li x La y TiO 3 , wherein 0<x<2 and 0<y<3, Li 2 O, LiOH, Li 2 CO 3 , LiAlO 2 , Li 2 O—Al 2 O 3 —SiO 2 —P 2 O 5 —TiO 2 —GeO 2 , or Li 3+x La 3 M 2 O 12 , wherein M is Te, Nb, or Zr, and 0≤x≤10.
18. A method of preparing an all-solid secondary battery, the method comprising:
providing a cathode layer comprising a cathode active material layer;
providing a first anode active material layer comprising an organic electrolyte and an anode active material that is capable of forming an alloy with lithium or a compound with lithium;
wherein the anode active material comprises at least one of a carbon-containing anode active material, a metal anode active material, or metalloid anode active material;
wherein the first anode active material layer comprises the organic electrolyte in a range from about 0.1 parts by weight to about 2.5 parts by weight, based on 100 parts by weight of the anode active material;
disposing the first anode active material layer on a solid electrolyte layer to prepare a stack; and
disposing the cathode layer on the solid electrolyte layer of the stack,
wherein the organic electrolyte comprises an organic salt comprising an organic cation and an anion,
wherein the organic cation comprises a heterocyclic cation comprising 1 to 3 heteroatoms, and
wherein an anode layer comprises a current collector and the first anode active material layer.
19. The method of claim 18 , further comprising:
disposing the first anode active material layer on a solid electrolyte layer to prepare a first stack;
disposing a second anode active material layer on the first anode active material layer to prepare a second stack; and
disposing a cathode layer on the solid electrolyte layer of the second stack,
wherein the second anode active material layer comprises a metal layer comprising lithium or a lithium alloy, and
wherein an anode layer comprises a current collector, the first anode active material layer, and the second anode active material layer.
20. A method of preparing an all-solid secondary battery, the method comprising:
providing a cathode layer comprising a cathode active material layer;
providing a first anode active material layer comprising an organic electrolyte and an anode active material that is capable of forming an alloy with lithium or a compound with lithium and a second anode active material layer comprising a metal layer comprising lithium or a lithium alloy;
wherein the anode active material comprises at least one of a carbon-containing anode active material, a metal anode active material, or metalloid anode active material;
wherein the first anode active material layer comprises the organic electrolyte in a range from about 0.1 parts by weight to about 2.5 parts by weight, based on 100 parts by weight of the anode active material;
disposing the first anode active material layer on the second anode active material layer to prepare a first stack;
disposing a solid electrolyte layer on the first anode active material layer of the first stack to prepare a second stack; and
disposing the cathode layer on the solid electrolyte layer of the second stack,
wherein the organic electrolyte comprises an organic salt comprising an organic cation and an anion,
wherein the organic cation comprises a heterocyclic cation comprising 1 to 3 heteroatoms, and
wherein an anode layer comprises a current collector, the first anode active material layer, and the second anode active material layer.