CN102903898B - A kind of graphite and transition metal oxide composite cathode material and preparation method thereof - Google Patents
A kind of graphite and transition metal oxide composite cathode material and preparation method thereof Download PDFInfo
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- CN102903898B CN102903898B CN201210398479.XA CN201210398479A CN102903898B CN 102903898 B CN102903898 B CN 102903898B CN 201210398479 A CN201210398479 A CN 201210398479A CN 102903898 B CN102903898 B CN 102903898B
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- 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 present invention is for solution graphite and transition metal oxide are as the technical problem existing for lithium ion battery negative material, disclosing a kind of graphite and transition metal oxide composite cathode material, is be (3 ~ 9) by mass ratio: graphite and the transition metal oxide of (1 ~ 7) are made.Preparation method is: take graphite, transition metal oxide, fully grind, mix, to obtain final product; In nitrogen atmosphere, carry out material with carbon-coated surface again, the chemical property of the composite negative pole material of the surperficial bag carbon obtained is better.Graphite prepared by the present invention and transition metal oxide composite cathode material, have good conductivity, and its capacity is higher than graphite cathode material, and high rate performance is also better than graphite; Fluffy graphite-structure also effectively can cushion the change in volume that transition metal oxide occurs in charge and discharge process; Do not carry out surperficial bag carbon and can have good cycle performance and high rate performance yet.
Description
Technical field
The present invention relates to a kind of graphite and transition metal oxide composite cathode material and preparation method thereof, belong to technical field of inorganic nonmetallic materials.
Background technology
Graphite has layer structure, and lithium ion to be easily combined with carbon atom at interlayer and to form intercalation compound Li
xc
6(x≤1), thus can repeatedly carry out the embedding of lithium and deviate from, corresponding theoretical specific capacity is 372mAh/g, is the main flow negative material of current commercial li-ion battery.Graphite is that electron conduction is good as the major advantage of negative material, charge and discharge potential is low, security performance is high, shortcoming is actual capacity lower (being about 300-330mAh/g), high rate performance is poor, the battery of its assembling can not meet current actual demand far away, the especially needs of electrokinetic cell.Although carry out doping vario-property or surface treatment to graphite, storage lithium ability is low is cause its actual capacity to be difficult to the basic reason improved.In order to meet the demand of high-energy power supply, exploring and there is high power capacity, long-life Novel cathode material for lithium ion battery, to substitute the graphite cathode material of current low capacity, have very important significance.
Transition metal oxide is as lithium ion battery negative material, and in charging process, transition metal oxide and lithium metal react and the transition metal restored; In discharge process, the metallic element restored again is oxidized to metal oxide and is restored by lithium again simultaneously, and Mechanism of electrochemical behaviors of anhydrous can be expressed as:
(M=Co, Ni, Cu, Fe etc.)
Transition metal oxide negative material theoretical capacity is higher, general at about 700mAh/g, good rate capability, fail safe is high, most of transition oxide abundant raw material source, cheap, environmental friendliness simultaneously, preparation is simple, and therefore transition metal oxide is the lithium ion battery cathode material that a class has development potentiality very much.But because metal conductive oxide is poor, and in charge and discharge process, change in volume is violent, causes its cycle performance poor, thus have impact on the actual practicality of transition metal oxide in lithium ion battery.At present, although take the measures such as nanometer, porous, carbon is coated to improve the cycle performance of transition metal oxide, but still be difficult to fundamentally to overcome the deficiency that its aspect of performance exists.
In conjunction with graphite and the Mechanism of electrochemical behaviors of anhydrous of transition metal oxide, respective performance advantage and weakness, of the present invention applicant proposed a kind ofly forms by graphite and transition metal oxide the technology that composite negative pole material improves lithium ion battery negative material chemical property.
Summary of the invention
For above-mentioned prior art, the present invention, for solving graphite and transition metal oxide as the technical problem existing for lithium ion battery negative material, provides and a kind ofly forms by graphite and transition metal oxide the technology that composite negative pole material improves lithium ion battery negative material chemical property.Graphite prepared by the present invention and transition metal oxide composite cathode material, have good conductivity, and its capacity is higher than graphite cathode material, and high rate performance is also better than graphite; Fluffy graphite-structure also effectively can cushion the change in volume that transition metal oxide occurs in charge and discharge process; Do not carry out surperficial bag carbon and can have good cycle performance and high rate performance yet.
The present invention is achieved by the following technical solutions:
A kind of graphite and transition metal oxide composite cathode material are be (3 ~ 9) by mass ratio: graphite and the transition metal oxide of (1 ~ 7) are made.
Described transition metal oxide is the binary oxide of the elements such as Fe, Mn, Co, Ni, Cu, Ti, W, Mo, V, Cr, and comprises ternary oxide and the multivariant oxide of these elements, as A
-xb
yo
z, wherein A=Mg, Ca, Na, K, Zn, Fe, Mn, Co, Ni, Cu, Ti, W, Mo, V, Cr etc., B=Fe, Mn, Co, Ni, Cu, Ti, W, Mo, V, Cr, Sn etc. also can be two or more mixtures in these oxides.
Preferably, the mass ratio of graphite and transition metal oxide is (1 ~ 4): 1.
The preparation method of described graphite and transition metal oxide composite cathode material is: take graphite, transition metal oxide, fully grind, mix, obtain composite negative pole material.
Preferably, the particle diameter of described graphite is 0.5 ~ 80 μm.
Preferably, when the particle diameter of described transition metal oxide is 10 ~ 200nm, chemical property is better.
Preferably, graphite and transition metal oxide ground and mixed evenly after, the composite negative pole material obtained carries out material with carbon-coated surface again in nitrogen atmosphere, and the chemical property of the composite negative pole material of the surperficial bag carbon obtained is better.
The described concrete grammar carrying out material with carbon-coated surface in nitrogen atmosphere is: graphite and transition metal oxide ground and mixed evenly after, add in the aqueous solution of glucose, wherein the mass ratio of glucose and composite negative pole material is (0.2 ~ 0.4): 1, the addition of water is good to cover solid union material, after mixing, 100 ~ 120 DEG C of oven dry, in nitrogen atmosphere, be then heated to 500 DEG C ~ 600 DEG C, be incubated 5 ~ 10 hours, obtain the composite negative pole material of surperficial bag carbon.
The present invention is for solution graphite and transition metal oxide are as the technical problem existing for lithium ion battery negative material, in conjunction with graphite and the Mechanism of electrochemical behaviors of anhydrous of transition metal oxide, respective performance advantage and weakness, provide and a kind ofly form by graphite and transition metal oxide the technology that composite negative pole material improves lithium ion battery negative material chemical property.Graphite prepared by the present invention and transition metal oxide composite cathode material, have good conductivity, and its capacity is higher than graphite cathode material, and high rate performance is also better than graphite; Fluffy graphite-structure also effectively can cushion the change in volume that transition metal oxide occurs in charge and discharge process; Do not carry out surperficial bag carbon and can have good cycle performance and high rate performance yet.
The invention has the beneficial effects as follows:
1, graphite and transition metal oxide composite cathode material preparation process simply, are easily controlled, and equipment investment is few, and energy consumption is low, and production efficiency is high.
2, the graphite prepared and transition metal oxide composite cathode material have good chemical property, and not only capacity is higher than graphite, and high rate performance is also better than graphite.
3, the graphite of preparation and the actual capacity of transition metal oxide composite cathode material can adjust easily according to the different ratio of the two.
4, the graphite prepared and transition metal oxide composite cathode material, do not carry out surperficial bag carbon and can have good cycle performance and high rate performance yet.
5, preparing graphite and transition metal oxide composite cathode material is carry out in air at room temperature, does not need protective atmosphere, can not change the composition and structure of oxide, ensure that the stability of graphite and metal oxide composite cathode material.
Although 6 transition metal oxide negative materials, in charge and discharge process, larger change in volume can occur, fluffy graphite-structure can play effective cushioning effect.
Accompanying drawing explanation
Fig. 1 is the x-ray diffraction pattern of carbon coated iron oxide/composite cathode material of silicon/carbon/graphite that embodiment 2 obtains.
Fig. 2 is the cycle performance of iron oxide/composite cathode material of silicon/carbon/graphite that embodiment 1 obtains.
Fig. 3 is the cycle performance of carbon coated graphite/iron oxide composite negative pole material that embodiment 2 obtains.
Fig. 4 is the high rate performance of carbon coated graphite/iron oxide composite negative pole material that embodiment 4 obtains.
Embodiment
Below in conjunction with embodiment, the present invention is further illustrated.
Embodiment 1 by iron oxide and graphite-made for iron oxide/composite cathode material of silicon/carbon/graphite
Preparation method is: weigh the iron oxide 0.6g getting particle diameter about 20nm in the balance, the graphite 2.4g of granularity about 20 μm, in mortar, fully grinding is even, obtain iron oxide/composite cathode material of silicon/carbon/graphite, after the aqueous solution prepared with 0.9g glucose 10 milliliters mixes, 105 DEG C of oven dry, then in nitrogen atmosphere, be heated to 500 DEG C, be incubated 5 hours, obtain the composite negative pole material of surperficial bag carbon.
As shown in Figure 2, the capacity recording its discharge and recharge 85 times under 0.1C multiplying power is 408.7mAh/g to the cycle performance of iron oxide/composite cathode material of silicon/carbon/graphite that the present embodiment obtains.
Embodiment 2 by iron oxide and graphite-made for iron oxide/composite cathode material of silicon/carbon/graphite
Preparation method is: weigh the iron oxide 0.9g getting particle diameter about 20nm in the balance, the graphite 2.1g of granularity about 20 μm, in mortar, fully grinding is even, obtain iron oxide/composite cathode material of silicon/carbon/graphite, after the aqueous solution prepared with 0.9g glucose 10 milliliters mixes, 120 DEG C of oven dry, then in nitrogen atmosphere, be heated to 550 DEG C, be incubated the composite negative pole material that 5 hours obtain surperficial bag carbon.
The battery of the carbon coated iron oxide that the present embodiment obtains/composite cathode material of silicon/carbon/graphite assembling, as shown in Figure 3, the capacity that discharge and recharge is 30 times is 497mAh/g to the cycle performance under 0.1C multiplying power.
The x-ray diffraction pattern of carbon coated iron oxide/composite cathode material of silicon/carbon/graphite that the present embodiment obtains, as only having graphite and iron oxide two kinds of thing phases in Fig. 1, figure, does not have other impurity.
Embodiment 3 by iron oxide and graphite-made for iron oxide/composite cathode material of silicon/carbon/graphite
Preparation method is: weigh the iron oxide 1.2g getting particle diameter about 20nm in the balance, the graphite 1.8g of granularity about 6 μm, in mortar, fully grinding is even, obtain iron oxide/composite cathode material of silicon/carbon/graphite, after the aqueous solution prepared with 0.9g glucose 10 milliliters mixes, 105 DEG C of oven dry, then in nitrogen atmosphere, be heated to 550 DEG C, be incubated 5 hours, obtain the composite negative pole material of surperficial bag carbon.The battery assembled by this carbon coated iron oxide/composite cathode material of silicon/carbon/graphite, the capacity recording its discharge and recharge 30 times under 0.1C multiplying power is 483mAh/g, under the discharge-rate of 0.1C, 0.2C, 0.5C, 1.0C, respectively carry out 10 charge and discharge cycles, capacity can reach 481.5 respectively, 463.4,357.7,287.4mAh g
-1.
Embodiment 4 by iron oxide and graphite-made for iron oxide/composite cathode material of silicon/carbon/graphite
Preparation method is: weigh the iron oxide 1.5g getting particle diameter about 50nm in the balance, the graphite 1.5g of granularity about 6 μm, in mortar, fully grinding is even, obtain iron oxide/composite cathode material of silicon/carbon/graphite, after the aqueous solution prepared with 0.9g glucose 10 milliliters mixes, 110 DEG C of oven dry, then in nitrogen atmosphere, be heated to 600 DEG C, be incubated 5 hours, obtain the composite negative pole material of surperficial bag carbon.The battery assembled by carbon coated iron oxide/composite cathode material of silicon/carbon/graphite, the capacity recording its discharge and recharge 30 times under 0.1C multiplying power is 475mAh/g.
The high rate performance of carbon coated iron oxide/composite cathode material of silicon/carbon/graphite that the present embodiment obtains is as Fig. 4, under the discharge-rate of 0.1C, 0.2C, 0.5C, 1.0C, 2.0C, respectively carry out 10 charge and discharge cycles, capacity can reach 472.4 respectively, 464,376,322.4,230mAh g
-1.
Embodiment 5 by manganese oxide and graphite-made for manganese oxide/composite cathode material of silicon/carbon/graphite
Preparation method is: weigh the manganese oxide 1.5g getting particle diameter about 50nm in the balance, the graphite 1.5g of granularity about 20 μm, and in mortar, fully grinding evenly, to obtain final product.The battery assembled by this composite material, the capacity of 55 times of circulating under 0.1C multiplying power is 452mAh/g.
Embodiment 6 by cupric oxide and graphite-made for cupric oxide/composite cathode material of silicon/carbon/graphite
Preparation method is: weigh the cupric oxide 1.5g getting particle diameter about 30nm in the balance, the graphite 1.5g of granularity about 20 μm, and in mortar, fully grinding evenly, to obtain final product.The battery assembled by this composite material, the capacity of 37 times of circulating under 0.1C multiplying power is 472mAh/g.
Embodiment 7 by cobalt oxide and graphite-made for cobalt oxide/composite cathode material of silicon/carbon/graphite
Preparation method: weigh the cobalt oxide 1.2g getting particle diameter about 60nm in the balance, the graphite 1.8g of granularity about 20 μm, in mortar, fully grinding evenly, to obtain final product.The battery assembled by this composite material, the capacity of 42 times of circulating under 0.1C multiplying power is 552.4mAh/g.
With accompanying drawing, the specific embodiment of the present invention is described although above-mentioned in conjunction with the embodiments; but not limiting the scope of the invention; one of ordinary skill in the art should be understood that; on the basis of technical scheme of the present invention, those skilled in the art do not need to pay various amendment or distortion that creative work can make still within protection scope of the present invention.
Claims (1)
1. the preparation method of the composite negative pole material of surperficial bag carbon: take graphite, a transition metal oxide, fully grind, mix, obtain composite negative pole material; The mass ratio of graphite and transition metal oxide is (1 ~ 4): 1, and the particle diameter of described graphite is 0.5 ~ 80 μm; The particle diameter of described transition metal oxide is 10 ~ 200nm; Composite negative pole material is added in the aqueous solution of glucose, wherein the mass ratio of glucose and composite negative pole material is (0.2 ~ 0.4): 1, the addition of water is good to cover solid union negative material, after mixing, 100 ~ 120 DEG C of oven dry, then in nitrogen atmosphere, be heated to 500 DEG C ~ 600 DEG C, be incubated 5 ~ 10 hours, obtain the composite negative pole material of surperficial bag carbon; Described transition metal oxide is iron oxide, manganese oxide, cupric oxide or cobalt oxide.
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Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6246682B2 (en) * | 2014-09-01 | 2017-12-13 | 日立オートモティブシステムズ株式会社 | Lithium ion secondary battery |
| CN105226242B (en) * | 2014-10-27 | 2017-12-26 | 湖南摩根海容新材料有限责任公司 | A kind of lithium ion battery negative material and preparation method thereof |
| CN105591092B (en) * | 2014-11-18 | 2019-02-26 | 中国科学院兰州化学物理研究所 | A kind of cobalt-nickel-manganese oxide compound lithium ion battery negative material and its preparation method and application |
| CN105702938B (en) * | 2016-04-15 | 2018-04-03 | 华南师范大学 | A kind of iron-based oxide lithium ion battery negative material and preparation method and application |
| CN105958069A (en) * | 2016-05-27 | 2016-09-21 | 雅安乾润锂电池材料有限公司 | Preparation method of graphite negative electrode material for lithium-ion battery |
| CN107017397A (en) * | 2017-06-01 | 2017-08-04 | 湖北工程学院 | Graphite composite material and application thereof, preparation method and lithium ion battery |
| CN109244392A (en) * | 2018-08-23 | 2019-01-18 | 武汉艾特米克超能新材料科技有限公司 | A kind of composite graphite negative electrode material and preparation method thereof and lithium ion battery |
| CN110931757A (en) * | 2019-12-16 | 2020-03-27 | 成都爱敏特新能源技术有限公司 | Graphite composite material and preparation method thereof |
| CN113258042A (en) * | 2021-04-22 | 2021-08-13 | 湖南镕锂新材料科技有限公司 | Graphite negative electrode material and preparation method and application thereof |
| CN113860351A (en) * | 2021-08-23 | 2021-12-31 | 中南大学 | Preparation method and application of CuO-graphite composite material prepared from waste graphite |
| CN114883537A (en) * | 2022-03-31 | 2022-08-09 | 格龙新材料科技(常州)有限公司 | High-capacity fast-charging negative electrode composite material and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1913200A (en) * | 2006-08-22 | 2007-02-14 | 深圳市贝特瑞电子材料有限公司 | Silicon carbone compound negative polar material of lithium ion battery and its preparation method |
-
2012
- 2012-10-19 CN CN201210398479.XA patent/CN102903898B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1913200A (en) * | 2006-08-22 | 2007-02-14 | 深圳市贝特瑞电子材料有限公司 | Silicon carbone compound negative polar material of lithium ion battery and its preparation method |
Non-Patent Citations (4)
| Title |
|---|
| Graphite-metal oxide composites as anode for Li-ion batteries;H. Huang et al;《Journal of Power Sources》;20010731(第97-98期);第114页左栏最后1段 * |
| Synthesis of CuO/grapheme nanocomposite as a high-performance anode material for lithium-ion batteries;Bao Wang et al;《Journal of Materials Chemistry》;20101011(第20期);第10661页右栏最后1段-第10662页左栏第1段 * |
| 低温锂离子电池负极材料的制备及其电化学性能研究;高杰;《中国博士学位论文全文数据库 工程科技Ⅱ辑》;20071215(第6期);第35、85-86、94-96页 * |
| 负极材料石墨/SnO2/无定形碳的电化学性能;张金章等;《电池》;20100831;第40卷(第4期);全文 * |
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