Composite graphite material and method for preparation thereof, secondary battery, and apparatus
The present application discloses a composite graphite material and a method for preparing the same, a secondary battery, and an apparatus. The composite graphite material includes a core material and a coating layer that coats at least a portion of the surface of the core material, the core material including graphite, and the coating layer including a coating material containing a cyclic structure moiety, wherein the composite graphite material has a weight-loss rate of from 0.1% to 0.55% when the composite graphite material is heated in an atmosphere of an inert non-oxidative gas at a temperature rising from 40° C. to 800° C. The composite graphite material can enhance the gram capability and reduce the expansion rate of an electrode plate, and more preferably, can improve the cycle performance and kinetic performance of a battery as well.
1. A composite graphite material, comprising a core material and a coating layer that coats at least a portion of the surface of the core material, characterized in that the core material comprises graphite, and the coating layer comprises a coating material containing a cyclic structure moiety, wherein the composite graphite material has a weight-loss rate of from 0.1% to 0.55% when the composite graphite material is heated at a heating rate of 10° C./min or lower in an atmosphere of an inert non-oxidative gas at a temperature rising from 40° C. to 800° C., and wherein the cyclic structure moiety comprises one or more of Formulae 1 to 3:
2. The composite graphite material according to claim 1 , characterized in that the composite graphite material has a weight-loss rate of from 0.1% to 0.4%, when the composite graphite material is heated at a heating rate of 10° C./min or lower in the atmosphere of an inert non-oxidative gas at a temperature rising from 40° C. to 800° C.
3. The composite graphite material according to claim 1 , characterized in that the composite graphite material has a sulfur content of less than 0.02 wt. %.
4. The composite graphite material according to claim 1 , characterized in that the core material is artificial graphite.
5. The composite graphite material according to claim 4 , characterized in that the composite graphite material has a D-peak intensity I D and a G-peak intensity I G , and the ratio of I D /I G is from 0.4 to 1.0.
6. The composite graphite material according to claim 4 , characterized in that the composite graphite material satisfies a ratio of the peak area C 004 of 004 crystal plane to the peak area C 110 of 110 crystal plane of the composite graphite material C 004 /C 110 ≤15, when the composite graphite material is in an electrode plate with a compaction density of from 1.6 g/cm 3 to 1.7 g/cm 3 .
7. The composite graphite material according to claim 4 , characterized in that the composite graphite material further satisfies one or more of the following (1) to (6):
(1) the composite graphite material has a D v 50 of from 15 μm to 20 μm;
(2) the composite graphite material has a D v 10 of at least 6 μm;
(3) the composite graphite material has a D n 10 of from 1.0 μm to 3.0 μm;
(4) the composite graphite material has a specific surface area of from 0.5 m 2 /g to 1.2 m 2 /g;
(5) the composite graphite material has a compaction density under a pressure of 5 tons of from 1.80 g/cm 3 to 2.10 g/cm 3 ; and
(6) the composite graphite material has a tap density of from 0.8 g/cm 3 to 1.15 g/cm 3 .
8. The composite graphite material according to claim 4 , characterized in that the composite graphite material further satisfies one or more of the following (1) to (6):
(1) the composite graphite material has a D v 50 of from 15 μm to 18 μm;
(2) the composite graphite material has a D v 10 of from 6.5 μm to 10.5 μm;
(3) the composite graphite material has a D n 10 of from 1.2 μm to 2.0 μm;
(4) the composite graphite material has a specific surface area of from 0.6 m 2 /g to 1.0 m 2 /g;
(5) the composite graphite material has a compaction density under a pressure of 5 tons of from 1.93 g/cm 3 to 2.05 g/cm 3 ; and
(6) the composite graphite material has a tap density of from 0.9 g/cm 3 to 1.05 g/cm 3 .
9. A method for preparing a composite graphite material, characterized in that the method comprises the steps of
(1) mixing a solution containing a cyclizable polymer with a graphite core material to obtain a slurry, wherein a mass ratio of the core material to the cyclizable polymer is from 30:1 to 400:1;
(2) drying the slurry to obtain powder;
(3) heat treating the powder at a temperature between 300° C. and 400° C. to obtain the composite graphite material comprising a core material and a coating layer that coats at least a portion of the surface of the core material,
wherein the core material comprises graphite, and the coating layer comprises a coating material containing a cyclic structure moiety, and wherein the composite graphite material has a weight-loss rate of from 0.1% to 0.55% when the composite graphite material is heated at a heating rate of 10° C./min or lower in an atmosphere of an inert non-oxidative gas at a temperature rising from 40° C. to 800° C., and wherein the cyclic structure moiety comprises one or more of Formulae 1 to 3:
10. The method according to claim 9 , characterized in that a mass ratio of the graphite core material to the cyclizable polymer, m G :m P , is from 40:1 to 200:1.
11. The method according to claim 9 , characterized in that the cyclizable polymer comprises one or more of polyacrylonitrile or copolymers thereof.
12. The method according to claim 9 , characterized in that the cyclizable polymer has a number average molecular weight of from 50,000 to 150,000 Da.
13. The method according to claim 9 , characterized in that in the step (3),
the powder is heat treated at a temperature between 350° C. and 400° C.; and/or
the heat treating time is from 3 hours to 6 hours.
14. A secondary battery comprising a negative electrode plate which comprises a negative active material, characterized in that the negative active material comprises a composite graphite material comprising a core material and a coating layer that coats at least a portion of the surface of the core material, characterized in that the core material comprises graphite, and the coating layer comprises a coating material containing a cyclic structure moiety, wherein the composite graphite material has a weight-loss rate of from 0.1% to 0.55% when the composite graphite material is heated at a heating rate of 10° C./min or lower in an atmosphere of an inert non-oxidative gas at a temperature rising from 40° C. to 800° C., and wherein the cyclic structure moiety comprises one or more of Formulae 1 to 3:
15. The secondary battery according to claim 14 , characterized in that the composite graphite material has a sulfur content of less than 0.02 wt. %.
16. The secondary battery according to claim 14 , characterized in that the core material is artificial graphite.
17. The secondary battery according to claim 16 , characterized in that the composite graphite material has a D-peak intensity I D and a G-peak intensity I G , and the ratio of I D /I G is from 0.4 to 1.0.
18. The secondary battery according to claim 16 , characterized in that the composite graphite material satisfies a ratio of the peak area C 004 of 004 crystal plane to the peak area C 110 of 110 crystal plane of the composite graphite material C 004 /C 110 ≤15, when the composite graphite material is in an electrode plate with a compaction density of from 1.6 g/cm 3 to 1.7 g/cm 3 .
19. The secondary battery according to claim 16 , characterized in that the composite graphite material further satisfies one or more of the following (1) to (6):
(1) the composite graphite material has a D v 50 of from 15 μm to 20 μm;
(2) the composite graphite material has a D v 10 of at least 6 μm;
(3) the composite graphite material has a D n 10 of from 1.0 μm to 3.0 μm;
(4) the composite graphite material has a specific surface area of from 0.5 m 2 /g to 1.2 m 2 /g;
(5) the composite graphite material has a compaction density under a pressure of 5 tons of from 1.80 g/cm 3 to 2.10 g/cm 3 ; and
(6) the composite graphite material has a tap density of from 0.8 g/cm 3 to 1.15 g/cm 3 .
20. The secondary battery according to claim 16 , characterized in that the composite graphite material further satisfies one or more of the following (1) to (6):
(1) the composite graphite material has a D v 50 of from 15 μm to 18 μm;
(2) the composite graphite material has a D v 10 of from 6.5 μm to 10.5 μm;
(3) the composite graphite material has a D n 10 of from 1.2 μm to 2.0 μm;
(4) the composite graphite material has a specific surface area of from 0.6 m 2 /g to 1.0 m 2 /g;
(5) the composite graphite material has a compaction density under a pressure of 5 tons of from 1.93 g/cm 3 to 2.05 g/cm 3 ; and
(6) the composite graphite material has a tap density of from 0.9 g/cm 3 to 1.05 g/cm 3 .