CN102646812A - Structure of cathode material of lithium ion battery - Google Patents
Structure of cathode material of lithium ion battery Download PDFInfo
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- CN102646812A CN102646812A CN2012101241114A CN201210124111A CN102646812A CN 102646812 A CN102646812 A CN 102646812A CN 2012101241114 A CN2012101241114 A CN 2012101241114A CN 201210124111 A CN201210124111 A CN 201210124111A CN 102646812 A CN102646812 A CN 102646812A
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- ion battery
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a structure of a cathode material of a lithium ion battery. The structure comprises an active substance layer, a loosened conducting layer and a hard shell conducting layer that are distributed radially in sequence, wherein the active substance layer and the hard shell conducting layer are communicated with each other by the loosened conducting layer, the loosened conducting layer is in an elastic memory structure, and the volume of the loosened conducting layer changes along with the change of the volume of the active substance layer. The structure adopts the radially-distributed three-layered structure, the loosened conducting layer serves as the middle layer, the volume of the loosened conducting layer changes along with the active substance layer, and therefore, the volume effect in the charging and discharging processes can be effectively reduced, the phenomena of pulverization and dropping of the cathode material can be relieved and even eliminated, thereby improving the specific capacity and the cycling stability of the battery.
Description
Technical field
The present invention relates to the battery technology field, be specifically related to a kind of structure of lithium ion battery negative material.
Background technology
Fast development along with microelectronics industry, automobile industry; And the popularizing of various portable communication apparatus, PC, miniaturized electronics, human requirement to lithium ion battery also develops towards high-energy-density, high power density, high security, long-life, fast charging and discharging, frivolous direction.At present, business-like lithium ion battery is a negative pole with graphite, the compound that contains lithium is anodal.Wherein, the theoretical specific capacity of graphite has only 372mAh/g, and this becomes the huge obstruction that improves the lithium ion battery performance.Therefore, the novel negative material of developing high power capacity in recent years becomes the research emphasis in lithium ion battery field.
At present, have the metal alloy of height ratio capacity and the concern that metal oxide causes the researcher.Compare with the conventional carbon negative material, they have high lithium storage content, silicon (4200mAh/g) for example, tin (994mAh/g), tin oxide (781mAh/g).But also there is bigger problem in they as lithium ion battery negative material: in the battery charge and discharge process, negative material produces serious volumetric expansion effect (silicon is up to 300%), can cause the electrode efflorescence, thereby reduces battery useful life; Battery repeatedly discharges and recharges and can cause that negative material reunites, and influences the cyclical stability of battery.The approach that addresses these problems at present mainly contains: 1. prepare the negative material of nano-scale, alleviate the volumetric expansion in the charge and discharge process; 2. inert matter and active lithium storage materials is compound, reduce the volumetric expansion of negative material, prevent the reunion of active material simultaneously; 3. the negative material for preparing special construction utilizes structural advantage to alleviate the volumetric expansion of negative material.
In existing research, many people have solved above problem to a certain extent.Chinese patent CN1402366A discloses a kind of Si-C-X composite negative pole material with nucleocapsid structure, and he can alleviate the reunion of active material and the volumetric expansion in the charge and discharge process to a certain extent.The researcher at first is dissolved in the carbon containing precursor earlier in the organic solvent, slowly adds the silicon alloy powder again, forms uniform solution.80 ℃ of organic solutions of volatilizing down, obtain silicon alloy-carbon precursor mixture.Again this mixture is calcined in inert atmosphere and obtained silicon alloy-carbon composite.It is in uneven thickness that but this method prepares the carbon coating layer of composite material, the adhesion between carbon-coating and the silicon alloy a little less than, carbon-coating separates, peels off with silicon alloy easily in the fast charging and discharging process, has a strong impact on the stable circulation performance of battery.
Summary of the invention
Problem to be solved by this invention provides a kind of GND structure that three-decker can guarantee that overall volume is constant that has, and overcomes the problems referred to above that exist in the prior art.
The structure of a kind of lithium ion battery negative material of the present invention; Comprise radially-arranged successively active material layer, loose conductive layer and duricrust conductive layer; Said active material layer and duricrust conductive layer are through said loose conductive layer UNICOM; The structure of said loose conductive layer is the elastic memory structure, and the volume of said loose conductive layer changes with the change in volume of said active material layer.The present invention adopts radially-arranged three-decker; And the conductive layer that will loosen changes with active material layer as its volume of intermediate layer; Therefore this structure can effectively reduce the bulk effect in the charge and discharge process; Efflorescence, the obscission of negative material alleviated even eliminated, thereby the specific capacity and the cyclical stability of battery improved.
The thickness of loose conductive layer according to the invention is 0.05～2um.
Loose conductive layer according to the invention is the dendritic structure layer that carbon fiber, CNT, RESEARCH OF PYROCARBON, Graphene or graphite constitute.
Loose conductive layer according to the invention is the filamentary structure layer that carbon fiber, CNT, RESEARCH OF PYROCARBON, Graphene or graphite constitute.
Loose conductive layer according to the invention is the cage structure layer that carbon fiber, CNT, RESEARCH OF PYROCARBON, Graphene or graphite constitute.
Loose conductive layer according to the invention is the network structure layer that carbon fiber, CNT, RESEARCH OF PYROCARBON, Graphene or graphite constitute.
Loose conductive layer according to the invention is the pumiceous texture layer that carbon fiber, CNT, RESEARCH OF PYROCARBON, Graphene or graphite constitute.
Nutty structure layer or the laminated structure layer of loose conductive layer according to the invention for constituting by carbon fiber, CNT, RESEARCH OF PYROCARBON, Graphene or graphite.
Duricrust conductive layer according to the invention is made up of dense carbon or carborundum, and its density is 1.8～2.0g/cm
3
The thickness of duricrust conductive layer according to the invention is 0.05～0.5um.
Through above technical scheme, the structure of a kind of lithium ion battery negative material of the present invention, it has three-decker, and its active material layer has higher lithium storage content, but at embedding/take off Li
+Volume can change a lot in the process, and exterior materials is produced very big pressure.Loose conductive layer is because its short texture is the elastic memory structure, when receiving the pressure of interior active material layer, and the effect that structure that can be through changing self and volume reach the bulk effect of buffers active material layer.Loose simultaneously conductive layer has good electrical conductivity, can guarantee active material layer and outside UNICOM.Duricrust conductive layer density is bigger, and quality is harder, has good electrical conductivity, can guarantee Li
+Quick embedding/deviate from, can guarantee the globality of material again.Simultaneously, because the active material layer skin is coated with material with carbon element, can effectively prevent the reunion of center material in the battery charge and discharge process, therefore the battery cyclical stability of lithium ion battery negative structure of the present invention is fabulous.
Description of drawings
Fig. 1 is the structure diagram of a kind of lithium ion battery negative material of the present invention.
Fig. 2 is the embedding of a kind of lithium ion battery negative material of the present invention/take off Li
+Principle schematic.
Fig. 3 is the GND structure of the loose conductive layer of dendroid.
Fig. 4 is the GND structure of fibrous loose conductive layer.
Fig. 5 is the GND structure of netted loose conductive layer.
Fig. 6 is the GND structure of the loose conductive layer of cage shape.
Fig. 7 is the GND structure of the loose conductive layer of graininess.
Fig. 8 is the GND structure of the loose conductive layer of sheet.
Fig. 9 is the GND structure of the loose conductive layer of foam-like.
Among the figure, 1, active material layer; 2, loose conductive layer; 3, the duricrust conductive layer.
Embodiment
As shown in Figure 1; The structure of a kind of lithium ion battery negative material of the present invention; Comprise radially-arranged successively active material layer 1, loose conductive layer 2 and duricrust conductive layer 3; Active material layer 1 passes through loose conductive layer 2 UNICOMs with duricrust conductive layer 3, and the structure of loose conductive layer 2 is the elastic memory structure, and the volume of loose conductive layer 2 changes with the change in volume of active material layer 1.。The present invention adopts radially-arranged three-decker; And the conductive layer that will loosen changes with active material layer as its volume of intermediate layer; Therefore this structure can effectively reduce the bulk effect in the charge and discharge process; Efflorescence, the obscission of negative material alleviated even eliminated, thereby the specific capacity and the cyclical stability of battery improved.
Above-mentioned active material layer 1 is sub-micron or nano level silicon, silicon monoxide, silicon dioxide, tin, tin monoxide, tin ash, copper, nickel, manganese, cobalt, antimony or lead, is the compound of above-mentioned substance perhaps, has higher lithium storage content.
Like Fig. 3-shown in Figure 9, the thickness of above-mentioned loose conductive layer 2 is 0.05～2um, is coated on the surface of active material layer 1 highly uniformly.It can be made up of conductive carbon materials such as carbon fiber, CNT, RESEARCH OF PYROCARBON, Graphene or graphite; Its shape can be the structure that dendroid, fibrous, cage shape, netted, graininess, sheet or foam-like etc. have elastic memory, can change with active material layer.
Above-mentioned duricrust conductive layer 3 is made up of dense carbon or carborundum, and its density is 1.8～2.0g/cm
3Thickness is 0.05～0.5um; Be coated on the surface of loose conductive layer 2 highly uniformly; It has the ability of good electrical conductivity and transmission lithium ion, has certain rigidity simultaneously, can bear certain pressure.
As shown in Figure 2, the lithium ion battery charge and discharge process with GND structure of the present invention is: lithium ion Li during discharge
+Embed, this moment, active material layer 1 volume in the lithium ion battery negative increased owing to the embedding of lithium ion, and 3 constancies of volume of duricrust conductive layer, then loose conductive layer 2 volumes increase, and guarantee whole constancy of volume; Lithium ion takes off embedding during charging, because disengaging active material layer 1 volume of lithium ion reduces, this moment, loose conductive layer 2 volumes then reduced to keep whole constancy of volume, had improved the cyclical stability of battery.Has the structure that memory rebounds and can make ability contraction distortions such as dendroid, fibrous, cage shape, netted or foam-like according to the structure that experiment showed, loose conductive layer 2.The present invention's conductive layer 2 that will loosen changes with active material layer 1 as its volume energy of intermediate layer; Therefore this structure can effectively reduce the bulk effect in the charge and discharge process; Efflorescence, the obscission of negative material alleviated even eliminated, thereby the specific capacity and the cyclical stability of battery improved.
Claims (10)
1. the structure of a lithium ion battery negative material; It is characterized in that: comprise radially-arranged successively active material layer, loose conductive layer and duricrust conductive layer; Said active material layer and duricrust conductive layer are through said loose conductive layer UNICOM; The structure of said loose conductive layer is the elastic memory structure, and the volume of said loose conductive layer changes with the change in volume of said active material layer.
2. the structure of a kind of lithium ion battery negative material according to claim 1 is characterized in that, the thickness of said loose conductive layer is 0.05～2um.
3. the structure of a kind of lithium ion battery negative material according to claim 1 is characterized in that, the dendritic structure layer of said loose conductive layer for being made up of carbon fiber, CNT, RESEARCH OF PYROCARBON, Graphene or graphite.
4. the structure of a kind of lithium ion battery negative material according to claim 1 is characterized in that, the filamentary structure layer of said loose conductive layer for being made up of carbon fiber, CNT, RESEARCH OF PYROCARBON, Graphene or graphite.
5. the structure of a kind of lithium ion battery negative material according to claim 1 is characterized in that, the cage structure layer of said loose conductive layer for being made up of carbon fiber, CNT, RESEARCH OF PYROCARBON, Graphene or graphite.
6. the structure of a kind of lithium ion battery negative material according to claim 1 is characterized in that, the network structure layer of said loose conductive layer for being made up of carbon fiber, CNT, RESEARCH OF PYROCARBON, Graphene or graphite.
7. the structure of a kind of lithium ion battery negative material according to claim 1 is characterized in that, the pumiceous texture layer of said loose conductive layer for being made up of carbon fiber, CNT, RESEARCH OF PYROCARBON, Graphene or graphite.
8. the structure of a kind of lithium ion battery negative material according to claim 1 is characterized in that, nutty structure layer or the laminated structure layer of said loose conductive layer for being made up of carbon fiber, CNT, RESEARCH OF PYROCARBON, Graphene or graphite.
9. the structure of a kind of lithium ion battery negative material according to claim 1 is characterized in that, said duricrust conductive layer is made up of dense carbon or carborundum, and density is 1.8～2.0g/cm
3
10. according to the structure of claim 1 or 8 described a kind of lithium ion battery negative materials, it is characterized in that the thickness of said duricrust conductive layer is 0.05～0.5um.
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Cited By (5)
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|---|---|---|---|---|
| CN103904335A (en) * | 2014-04-21 | 2014-07-02 | 哈尔滨工业大学 | Lithium ion battery negative material structure and preparation method thereof |
| CN104600248A (en) * | 2014-12-26 | 2015-05-06 | 中天科技精密材料有限公司 | Silicon-base negative material for lithium ion battery and preparation method of silicon-base negative material |
| CN108232139A (en) * | 2017-12-20 | 2018-06-29 | 中国科学院福建物质结构研究所 | A kind of graphene composite material and preparation method thereof |
| CN109103425A (en) * | 2012-08-29 | 2018-12-28 | 苏州宝时得电动工具有限公司 | Negative electrode material, cathode and the battery with the cathode |
| CN111430691B (en) * | 2020-03-31 | 2021-12-07 | 北京卫蓝新能源科技有限公司 | Silicon-based negative electrode material of lithium ion battery and preparation method thereof |
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| CN108232139B (en) * | 2017-12-20 | 2020-08-28 | 中国科学院福建物质结构研究所 | Graphene composite material and preparation method thereof |
| CN111430691B (en) * | 2020-03-31 | 2021-12-07 | 北京卫蓝新能源科技有限公司 | Silicon-based negative electrode material of lithium ion battery and preparation method thereof |
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Application publication date: 20120822 |