Three-dimensional batteries with compressible cathodes
A secondary battery for cycling between a charged and a discharged state is provided. The secondary battery has an electrode assembly having a population of anode structures, a population of cathode structures, and an electrically insulating microporous separator material. The electrode assembly also has a set of electrode constraints that at least partially restrains growth of the electrode assembly. Members of the anode structure population have a first cross-sectional area, A 1 when the secondary battery is in the charged state and a second cross-sectional area, A 2 , when the secondary battery is in the discharged state, and members of the cathode structure population have a first cross-sectional area, C 1 when the secondary battery is in the charged state and a second cross-sectional area, C 2 , when the secondary battery is in the discharged state, where A 1 is greater than A 2 , and C 1 is less than C 2 .
1. A secondary battery for cycling between a charged state and a discharged state, the secondary battery comprising a battery enclosure, an electrode assembly, carrier ions, and a non-aqueous liquid electrolyte within the battery enclosure,
the electrode assembly comprising a population of anode structures, a population of cathode structures, and an electrically insulating microporous separator material electrically separating members of the population of anode structures and the population of cathode structures,
the population of anode structures and the population of cathode structures are arranged in an alternating sequence in a longitudinal direction, each member of the population of anode structures has a first cross-sectional area, A 1 , when the secondary battery is in the charged state and a second cross-sectional area, A 2 , when the secondary battery is in the discharged state,
each member of the population of cathode structures has a first cross-sectional area, C 1 , when the secondary battery is in the charged state and a second cross-sectional area, C 2 , when the secondary battery is in the discharged state, and the first cross-sectional area and the second cross-sectional area of the members of the population of anode structures and of the population of cathode structures, are measured in a first longitudinal plane parallel to the longitudinal direction;
the electrode assembly further comprising a set of electrode constraints that at least partially restrains growth of the electrode assembly in the longitudinal direction upon cycling of the secondary battery between the charged state and discharged state; and
each member of the population of cathode structures comprises a layer of a cathode active material comprising filler particles that are compressible and elastic, and each member of the population of anode structures comprises a layer of an anode active material having a capacity to accept more than one mole of carrier ion per mole of anode active material when the secondary battery is charged from the discharged state to the charged state,
A 1 being greater than A 2 for each of the members of a subset of the population of anode structures and C 1 is less than C 2 for each of the members of a subset of the population of cathode structures, and a difference C 2 −C 1 does not exceed a difference A 1 −A 2 during the cycling of the secondary battery.
2. The secondary battery of claim 1 , wherein the charged state is at least 75% of a rated capacity of the secondary battery, and the discharged state is less than 25% of the rated capacity of the secondary battery.
3. The secondary battery of claim 1 , wherein a ratio C 2 to C 1 for each member of the subset of the population of cathode structures is at least 1.1:1.
4. The secondary battery of claim 1 , wherein the subset of the population of anode structures has (a) a first median cross-sectional area MA A1 when the secondary battery is in the charged state and (b) a second median cross-sectional area MA A2 when the secondary battery is in the discharged state, and the subset of the population of cathode structures has a first median cross-sectional area MA C1 (c) when the secondary battery is in the charged state and (d) a second median cross-sectional area MA C2 when the secondary battery is in the discharged state, wherein MA A1 is greater than MA A2 and MA C1 is less than MA C2 .
5. The secondary battery of claim 1 , wherein at least one member of the subset of the population of anode structure has (a) a first median cross-sectional area ML A1 when the secondary battery is in the charged state, and (b) a second median cross-sectional area ML A2 when the secondary battery is in the discharged state, and at least one member of the subset of the population of cathode structure has (c) a first median cross-sectional area ML C1 when the secondary battery is in the charged state, and (d) a second median cross-sectional area ML C2 when the secondary battery is in the discharged state, wherein ML A1 , ML A2 , ML C1 and ML C2 , are measured in a plurality of longitudinal planes parallel to the longitudinal direction for each member, and
wherein ML A1 is greater than ML A2 for each of the members of the subset of the population of anode structures and ML C1 is less than ML C2 for each of the members of the subset of the population of cathode structures.
6. The secondary battery of claim 1 , wherein members of the population of cathode structures comprise a layer of cathode active material that is porous, and wherein the layer of cathode active material has a first porosity P 1 when the secondary battery is in a charged state, and a second porosity P 2 when the secondary battery is in a discharged state, the first porosity P 1 being less than the second porosity P 2 .
7. The secondary battery of claim 1 , wherein the cathode active material of members of the population of cathode structures comprise particles of cathode active materials dispersed in a matrix.
8. The secondary battery of claim 7 , wherein the cathode active material comprises particles of the cathode active material selected from the group consisting of transition metal oxides, transition metal sulfides, transition metal nitrides, lithium-transition metal oxides, lithium-transition metal sulfides, and lithium-transition metal nitrides, dispersed in the matrix, the matrix comprising a polymeric material.
9. The secondary battery of claim 1 , wherein the set of electrode constraints comprises:
a primary constraint system comprising first and second primary growth constraints and at least one primary connecting member,
the first and second primary growth constraints separated from each other in the longitudinal direction and the at least one primary connecting member connecting the first and second primary growth constraints, wherein the primary constraint system at least partially restrains growth of the electrode assembly in the longitudinal direction upon cycling of the secondary battery.
10. The secondary battery of claim 9 , wherein the set of electrode constraints further comprises:
a secondary constraint system comprising first and second secondary growth constraints separated in a second direction and connected by at least one secondary connecting member,
wherein the secondary constraint system at least partially restrains growth of the electrode assembly in a second direction upon cycling of the secondary battery, the second direction being orthogonal to the longitudinal direction.
11. A secondary battery for cycling between a charged state and a discharged state, the secondary battery comprising a battery enclosure, an electrode assembly, carrier ions, and a non-aqueous liquid electrolyte within the battery enclosure,
the electrode assembly comprising a population of anode structures, a population of cathode structures, and an electrically insulating microporous separator material electrically separating members of the population of anode structures and the population of cathode structures,
the population of anode structures and population of cathode structures are arranged in an alternating sequence in a longitudinal direction, each member of the population of anode structures has a first cross-sectional area, A 1 , when the secondary battery is in the charged state and a second cross-sectional area, A 2 , when the secondary battery is in the discharged state,
each member of the population of cathode structures has a first cross-sectional area, C 1 , when the secondary battery is in the charged state and a second cross-sectional area, C 2 , when the secondary battery is in the discharged state, and the first cross-sectional area and the second cross-sectional area of the members of the population of anode structures and of the population of cathode structures, are measured in a first longitudinal plane that is parallel to the longitudinal direction;
the electrode assembly further comprising a set of electrode constraints that at least partially restrains growth of the electrode assembly in the longitudinal direction upon cycling of the secondary battery between the charged state and the discharged state;
each member of the population of cathode structures comprising a layer of a cathode active material comprising filler particles, and each member of the population of anode structures comprises a layer of an anode active material having a capacity to accept more than one mole of carrier ion per mole of anode active material when the secondary battery is charged from a discharged state to a charged state,
a ratio C 2 to C 1 for each of the members of a subset of the population of cathode structures being at least 1.1 to 1 (1.1:1),
A 1 being greater than A 2 for each of the members of a subset of the population of anode structures and C 1 is less than C 2 for each of the members of the subset of the population of cathode structures, and a difference C 2 −C 1 does not exceed a difference A 1 −A 2 during cycling of the secondary battery.
12. The secondary battery of claim 11 , wherein the charged state is at least 75% of a rated capacity of the secondary battery, and the discharged state is less than 25% of the rated capacity of the secondary battery.
13. The secondary battery of claim 11 , wherein the filler particles of the layer of the cathode active material are compressible and elastic.
14. The secondary battery of claim 11 , wherein the subset of the population of anode structures has (a) a first median cross-sectional area MA A1 when the secondary battery is in the charged state and (b) a second median cross-sectional area MA A2 when the secondary battery is in the discharged state, and the subset of the population of cathode structure has (c) a first median cross-sectional area MA C1 when the secondary battery is in the charged state and (d) a second median cross-sectional area MA C2 when the secondary battery is in the discharged state, wherein MA A1 is greater than MA A2 and MA C1 is less than MA C2 .
15. The secondary battery of claim 11 , wherein at least one member of the subset of the population of anode structures has (a) a first median cross-sectional area ML A1 when the secondary battery is in the charged state, and (b) a second median cross-sectional area ML A2 when the secondary battery is in the discharged state, and at least one member of the subset of the population of cathode structure has (c) a first median cross-sectional area ML C1 when the secondary battery is in the charged state, and (d) a second median cross-sectional area ML C2 when the secondary battery is in the discharged state, where ML A1 , ML A2 , ML C1 and ML C2 , are measured in a plurality of longitudinal planes parallel to the longitudinal direction for each member, and
wherein ML A1 is greater than ML A2 for each of the members of the subset of the population of anode structures and ML C1 is less than ML C2 for each of the members of the subset of the population of cathode structures.
16. The secondary battery of claim 11 , wherein members of the population of cathode structures comprise a layer of cathode active material that is porous, and wherein the layer of cathode active material has a first porosity P 1 when the secondary battery is in a charged state, and a second porosity P 2 when the secondary battery is in a discharged state, the first porosity P 1 being less than the second porosity P 2 .
17. The secondary battery of claim 11 , wherein the cathode active material layers of members of the population of cathode structures comprise particles of cathode active materials dispersed in a matrix.
18. The secondary battery of claim 17 , wherein the cathode active material comprises particles of cathode active material selected from the group consisting of transition metal oxides, transition metal sulfides, transition metal nitrides, lithium-transition metal oxides, lithium-transition metal sulfides, and lithium-transition metal nitrides, dispersed in the matrix, the matrix comprising a polymeric material.
19. The secondary battery of claim 11 , wherein the set of electrode constraints comprises:
a primary constraint system comprising first and second primary growth constraints and at least one primary connecting member,
the first and second primary growth constraints separated from each other in the longitudinal direction and the at least one primary connecting member connecting the first and second primary growth constraints, wherein the primary constraint system at least partially restrains growth of the electrode assembly in the longitudinal direction upon cycling of the secondary battery.
20. The secondary battery of claim 19 , wherein the set of electrode constraints further comprises:
a secondary constraint system comprising first and second secondary growth constraints separated in a second direction and connected by at least one secondary connecting member,
wherein the secondary constraint system at least partially restrains growth of the electrode assembly in a second direction upon cycling of the secondary battery, the second direction being orthogonal to the longitudinal direction.