CN104466104A - Germanium-graphene composite cathode material for lithium ion battery and preparation method thereof - Google Patents
Germanium-graphene composite cathode material for lithium ion battery and preparation method thereof Download PDFInfo
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- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
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- 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 germanium-graphene composite cathode material for a lithium ion battery and a preparation method of the germanium-graphene composite cathode material. The composite cathode material is prepared from germanium particles and grapheme through compounding, wherein the nano germanium particles are uniformly distributed in a grapheme sheet layer to form a grapheme network cladded three-dimensional net structure. The preparation method comprises the following steps: (1) stirring and dispersing; (2) carrying out microwave hydrothermal; and (3) washing, drying and collecting. According to the germanium-graphene composite cathode material for the lithium ion battery and the preparation method of the germanium-graphene composite cathode material, germanium and germanium dioxide are re-crystallized and grow on the graphene in situ, the bonding strength of the germanium and the grapheme is higher than that of germanium-graphene composite material obtained through mixing simply, the electrical conductivity of the grapheme network is fully exerted, and the volume effect of the germanium is effectively inhibited. The germanium-graphene composite cathode material for the lithium ion battery has the characteristics of high capacity, high magnification and excellent cycling stability, the preparation process adopts simple and effective microwave hydrothermal reaction, the process is simple, the energy consumption is low, the yield is high, no pollution is caused, the germanium-graphene composite cathode material can be promoted and applied conveniently and is suitable for large-scale production.
Description
Technical field
The present invention relates to cell negative electrode material field technique, refer in particular to a kind of lithium ion battery germanium graphene composite negative pole and preparation method thereof.
Background technology
Current commercial lithium ion battery adopts graphite-like material with carbon element as negative material in a large number, because graphite-like material with carbon element exists lower specific discharge capacity, (its theoretical value is 372mAh/g, actual performance capacity is 330-360mAh/g) and poor high-rate charge-discharge capability, limit the raising of capacity of lithium ion battery.For satisfied future is civilian, the demand to high-capacity and long-life lithium ion battery such as industry or national defence, researcher is constantly exploring the carbon substitution material of other high power capacity, as metal and alloy type material.Wherein, germanium metal storage lithium theoretical specific capacity is up to 1600mAh/g, far above graphite negative electrodes material, and the diffusion velocity of lithium ion in germanium is 400 times in silicon, can meet at present for high power capacity, high magnification, eco-friendly lithium ion battery growth requirement.But pure germanium electrode material and other material types such as silicon, tin are like meeting owing to can be attended by 2-3 volumetric expansion doubly in embedding lithium and de-lithium process, efflorescence departs from collector and causes electrode cycle degradation, thus hinders its practical application.The Graphene of performance outstanding with the specific area, the specific strength of superelevation, outstanding conductivity etc. with super large for Ge particle is combined and forms composite construction and play and act synergistically, the Graphene network of high connductivity and high-specific surface area can suppress the pure germanium electrode powder phenomenon-tion that change in volume causes in charge and discharge cyclic process, while making electrode active material keep high power capacity, there is stable cycle performance and high rate performance.Patent CN 103247803 A discloses a kind of graphene coated Ge composite material and its preparation method and application, adopt the preparation of dielectric barrier discharge plasma auxiliary high-energy ball-milling method, although the method technique is simple, power consumption is large, is difficult to heavy industrialization.
Summary of the invention
In view of this, the present invention is directed to the disappearance of prior art existence, its main purpose is to provide a kind of lithium ion battery germanium graphene composite negative pole and preparation method thereof, it adopts microwave-hydrothermal method by germanium in-situ deposition on graphenic surface, the Volumetric expansion of material in charge and discharge process be alleviated or be suppressed to the existence of Graphene can, thus improve charge and discharge cycles stability and the high rate performance of its electrode material.
For achieving the above object, the present invention adopts following technical scheme:
A kind of lithium ion battery germanium graphene composite negative pole, be composited by the germanium particle of 50nm ~ 100nm and the Graphene of single or multiple lift, wherein, be distributed in graphene sheet layer to Ge uniform particles, formed by the coated three-dimensional net structure of Graphene network.
A preparation method for lithium ion battery germanium graphene composite negative pole, includes following steps:
(1) dispersed with stirring
Germanium powder 20 ~ 80 weight portion, germanium dioxide powder 20 ~ 80 weight portion, graphene powder 1 ~ 20 weight portion and distilled water 100 ~ 1000 weight portion are carried out ultrasonic agitation 5 ~ 30 minutes in mixer;
(2) microwave hydrothermal
Step (1) gained liquid is proceeded in the hydrothermal reaction kettle with Teflon liner, in microwave hydrothermal reaction and at 100 ~ 300 DEG C, processes 10 ~ 100 minutes;
(3) washing is dry collects
By step (2) products obtained therefrom collecting by filtration and by deionized water and ethanol cyclic washing 1 ~ 5 time, then in drier, adopt 50 ~ 100 DEG C of drying 5 ~ 10 h, germanium graphene composite negative pole can be obtained.
As a kind of preferred version, the purity of described germanium powder and germanium dioxide powder is more than 99.99%.
As a kind of preferred version, described Graphene adopts oxidation-reduction method, mechanical stripping method, epitaxial growth method, chemical vapour deposition technique, electrochemical process or arc process to obtain.
The present invention compared with prior art has obvious advantage and beneficial effect, specifically, as shown from the above technical solution:
Germanium graphene composite negative pole prepared by the present invention be through germanium and germanium dioxide again crystallization growth in situ on Graphene, the germanium graphene composite material of the bond strength mixing simple relative to other of germanium and Graphene is much larger, what the conductivity of Graphene network was played is more abundant, more effectively can suppress the bulk effect of germanium.Germanium graphene composite negative pole prepared by the present invention has taken into account high power capacity, high magnification and excellent cyclical stability feature, and preparation process adopts simple and effective microwave hydrothermal to react, and technique is simple, power consumption is few, and output is high, pollution-free, easy to utilize, be suitable for large-scale production.
For more clearly setting forth architectural feature of the present invention and effect, below in conjunction with accompanying drawing and specific embodiment, the present invention is described in detail.
Accompanying drawing explanation
Fig. 1 is the preparation flow schematic diagram of the preferred embodiment of the present invention.
Embodiment
The present invention discloses a kind of lithium ion battery germanium graphene composite negative pole, be composited by the germanium particle of 50nm ~ 100nm and the Graphene of single or multiple lift, wherein, be distributed in graphene sheet layer to Ge uniform particles, formed by the coated three-dimensional net structure of Graphene network.
The preparation method of described lithium ion battery germanium graphene composite negative pole is as follows: include following steps:
(1) dispersed with stirring
Germanium powder 20 ~ 80 weight portion, germanium dioxide powder 20 ~ 80 weight portion, graphene powder 1 ~ 20 weight portion and distilled water 100 ~ 1000 weight portion are carried out ultrasonic agitation 5 ~ 30 minutes in mixer, in the present embodiment, the purity of described germanium powder and germanium dioxide powder is more than 99.99%, and described Graphene adopts oxidation-reduction method, mechanical stripping method, epitaxial growth method, chemical vapour deposition technique, electrochemical process or arc process to obtain.
(2) microwave hydrothermal
Step (1) gained liquid is proceeded in the hydrothermal reaction kettle with Teflon liner, in microwave hydrothermal reaction and at 100 ~ 300 DEG C, processes 10 ~ 100 minutes.
(3) washing is dry collects
By step (2) products obtained therefrom collecting by filtration and by deionized water and ethanol cyclic washing 1 ~ 5 time, then in drier, adopt 50 ~ 100 DEG C of drying 5 ~ 10 h, germanium graphene composite negative pole can be obtained.
The present invention will be described to use specific embodiment below:
Embodiment 1
(1) dispersed with stirring
Germanium powder 20 weight portion, germanium dioxide powder 70 weight portion, graphene powder 10 weight portion and distilled water 500 weight portion are carried out ultrasonic agitation 5 minutes in mixer.
(2) microwave hydrothermal
Step (1) gained liquid is proceeded in the hydrothermal reaction kettle with Teflon liner, in microwave hydrothermal reaction and at 100 DEG C, processes 10 minutes.
(3) washing is dry collects
By step (2) products obtained therefrom collecting by filtration and by deionized water and ethanol cyclic washing 2 times, then in drier, adopt 80 DEG C of drying 5 h, germanium graphene composite negative pole can be obtained.
Embodiment 2
(1) dispersed with stirring
Germanium powder 32 weight portion, germanium dioxide powder 69 weight portion, graphene powder 15 weight portion and distilled water 600 weight portion are carried out ultrasonic agitation 10 minutes in mixer.
(2) microwave hydrothermal
Step (1) gained liquid is proceeded in the hydrothermal reaction kettle with Teflon liner, in microwave hydrothermal reaction and at 120 DEG C, processes 30 minutes.
(3) washing is dry collects
By step (2) products obtained therefrom collecting by filtration and by deionized water and ethanol cyclic washing 3 times, then in drier, adopt 50 DEG C of drying 6 h, germanium graphene composite negative pole can be obtained.
Embodiment 3
(1) dispersed with stirring
Germanium powder 41 weight portion, germanium dioxide powder 50 weight portion, graphene powder 9 weight portion and distilled water 100 weight portion are carried out ultrasonic agitation 12 minutes in mixer.
(2) microwave hydrothermal
Step (1) gained liquid is proceeded in the hydrothermal reaction kettle with Teflon liner, in microwave hydrothermal reaction and at 150 DEG C, processes 20 minutes.
(3) washing is dry collects
By step (2) products obtained therefrom collecting by filtration and by deionized water and ethanol cyclic washing 1 time, then in drier, adopt 60 DEG C of drying 5.5 h, germanium graphene composite negative pole can be obtained.
Embodiment 4
(1) dispersed with stirring
Germanium powder 50 weight portion, germanium dioxide powder 42 weight portion, graphene powder 8 weight portion and distilled water 700 weight portion are carried out ultrasonic agitation 15 minutes in mixer.
(2) microwave hydrothermal
Step (1) gained liquid is proceeded in the hydrothermal reaction kettle with Teflon liner, in microwave hydrothermal reaction and at 200 DEG C, processes 40 minutes.
(3) washing is dry collects
By step (2) products obtained therefrom collecting by filtration and by deionized water and ethanol cyclic washing 4 times, then in drier, adopt 70 DEG C of drying 7 h, germanium graphene composite negative pole can be obtained.
Embodiment 5
(1) dispersed with stirring
Germanium powder 58 weight portion, germanium dioxide powder 41 weight portion, graphene powder 1 weight portion and distilled water 700 weight portion are carried out ultrasonic agitation 18 minutes in mixer.
(2) microwave hydrothermal
Step (1) gained liquid is proceeded in the hydrothermal reaction kettle with Teflon liner, in microwave hydrothermal reaction and at 210 DEG C, processes 50 minutes.
(3) washing is dry collects
By step (2) products obtained therefrom collecting by filtration and by deionized water and ethanol cyclic washing 3 times, then in drier, adopt 82 DEG C of drying 8 h, germanium graphene composite negative pole can be obtained.
Embodiment 6
(1) dispersed with stirring
Germanium powder 65 weight portion, germanium dioxide powder 20 weight portion, graphene powder 15 weight portion and distilled water 800 weight portion are carried out ultrasonic agitation 20 minutes in mixer.
(2) microwave hydrothermal
Step (1) gained liquid is proceeded in the hydrothermal reaction kettle with Teflon liner, in microwave hydrothermal reaction and at 240 DEG C, processes 65 minutes.
(3) washing is dry collects
By step (2) products obtained therefrom collecting by filtration and by deionized water and ethanol cyclic washing 5 times, then in drier, adopt 90 DEG C of dry 9h, germanium graphene composite negative pole can be obtained.
Embodiment 7
(1) dispersed with stirring
Germanium powder 73 weight portion, germanium dioxide powder 30 weight portion, graphene powder 18 weight portion and distilled water 1000 weight portion are carried out ultrasonic agitation 25 minutes in mixer.
(2) microwave hydrothermal
Step (1) gained liquid is proceeded in the hydrothermal reaction kettle with Teflon liner, in microwave hydrothermal reaction and at 260 DEG C, processes 80 minutes.
(3) washing is dry collects
By step (2) products obtained therefrom collecting by filtration and by deionized water and ethanol cyclic washing 3 times, then in drier, adopt 95 DEG C of drying 9 h, germanium graphene composite negative pole can be obtained.
Embodiment 8
(1) dispersed with stirring
Germanium powder 80 weight portion, germanium dioxide powder 80 weight portion, graphene powder 20 weight portion and distilled water 900 weight portion are carried out ultrasonic agitation 30 minutes in mixer.
(2) microwave hydrothermal
Step (1) gained liquid is proceeded in the hydrothermal reaction kettle with Teflon liner, in microwave hydrothermal reaction and at 300 DEG C, processes 100 minutes.
(3) washing is dry collects
By step (2) products obtained therefrom collecting by filtration and by deionized water and ethanol cyclic washing 5 times, then in drier, adopt 100 DEG C of drying 10 h, germanium graphene composite negative pole can be obtained.
Comparative example 1
Conventional graphite material.
Comparative example 2
The conventional composite material using Ge and Graphene to mix according to a certain percentage.
For detecting the performance of the lithium ion battery negative material of ionic liquid coated graphite negative material of the present invention, test by half-cell method of testing, negative material by above embodiment and comparative example: SBR (solid content 50%): CMC: Super-p=95.5: 2: 1.5: 1 (weight ratio), add appropriate amount of deionized water and reconcile into pulpous state, to coat on Copper Foil and within 12 hours, to make negative plate in vacuum drying chamber inner drying, , electrolyte is 1M LiPF6/EC+DEC+DMC=1: 1: 1, microporous polypropylene membrane is barrier film, be lithium sheet to electrode, be assembled into battery.Carry out constant current charge-discharge experiment at LAND battery test system, charging/discharging voltage is limited in 0.01 ~ 3.0 V, and the discharge and recharge cabinet computerizedd control carries out collection and the control of data, and the data obtained are as shown in table 1 below:
The negative material of preparation of the embodiment 1 ~ 8 that table 1 represents and the chemical property of comparative example 1,2 negative material
As can be seen from Table 1, prepared germanium graphene composite negative pole, has excellent volumetric properties, cycle performance and rate charge-discharge performance.
Design focal point of the present invention is: germanium graphene composite negative pole prepared by the present invention be through germanium and germanium dioxide again crystallization growth in situ on Graphene, the germanium graphene composite material of the bond strength mixing simple relative to other of germanium and Graphene is much larger, what the conductivity of Graphene network was played is more abundant, more effectively can suppress the bulk effect of germanium.Germanium graphene composite negative pole prepared by the present invention has taken into account high power capacity, high magnification and excellent cyclical stability feature, and preparation process adopts simple and effective microwave hydrothermal to react, and technique is simple, power consumption is few, and output is high, pollution-free, easy to utilize, be suitable for large-scale production.
The above, it is only preferred embodiment of the present invention, not technical scope of the present invention is imposed any restrictions, thus every above embodiment is done according to technical spirit of the present invention any trickle amendment, equivalent variations and modification, all still belong in the scope of technical solution of the present invention.
Claims (4)
1. a lithium ion battery germanium graphene composite negative pole, it is characterized in that: be composited by the germanium particle of 50nm ~ 100nm and the Graphene of single or multiple lift, wherein, be distributed in graphene sheet layer to Ge uniform particles, formed by the coated three-dimensional net structure of Graphene network.
2. a preparation method for lithium ion battery germanium graphene composite negative pole, is characterized in that: include following steps:
(1) dispersed with stirring
Germanium powder 20 ~ 80 weight portion, germanium dioxide powder 20 ~ 80 weight portion, graphene powder 1 ~ 20 weight portion and distilled water 100 ~ 1000 weight portion are carried out ultrasonic agitation 5 ~ 30 minutes in mixer;
(2) microwave hydrothermal
Step (1) gained liquid is proceeded in the hydrothermal reaction kettle with Teflon liner, in microwave hydrothermal reaction and at 100 ~ 300 DEG C, processes 10 ~ 100 minutes;
(3) washing is dry collects
By step (2) products obtained therefrom collecting by filtration and by deionized water and ethanol cyclic washing 1 ~ 5 time, then in drier, adopt 50 ~ 100 DEG C of drying 5 ~ 10 h, germanium graphene composite negative pole can be obtained.
3. the preparation method of a kind of lithium ion battery germanium graphene composite negative pole according to claim 2, is characterized in that: the purity of described germanium powder and germanium dioxide powder is more than 99.99%.
4. the preparation method of a kind of lithium ion battery germanium graphene composite negative pole according to claim 2, is characterized in that: described Graphene adopts oxidation-reduction method, mechanical stripping method, epitaxial growth method, chemical vapour deposition technique, electrochemical process or arc process to obtain.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104979533A (en) * | 2015-04-17 | 2015-10-14 | 重庆大学 | Graphene nano-belt wound germanium nanoparticle composite material preparation method |
| CN106099066A (en) * | 2016-08-09 | 2016-11-09 | 商丘师范学院 | A kind of germanium dioxide/graphene composite material and preparation method thereof |
| CN107673307A (en) * | 2016-08-01 | 2018-02-09 | 福建新峰二维材料科技有限公司 | Germanium/graphene/titanium dioxide nanofiber composite material and preparation method thereof and battery |
| CN109599536A (en) * | 2017-09-30 | 2019-04-09 | 天津大学 | Germanium hydrogen/redox graphene/conductive black nano composite lithium ion cell negative electrode material and preparation method thereof |
| CN110707303A (en) * | 2019-10-15 | 2020-01-17 | 商丘师范学院 | Ionic liquid/germanium quantum dot composite material and preparation method and application thereof |
| CN111640927A (en) * | 2020-06-17 | 2020-09-08 | 中国人民解放军国防科技大学 | Graphene-bridged polythiophene-coated germanium nanoparticle composite material and preparation method and application thereof |
| CN113991116A (en) * | 2021-10-22 | 2022-01-28 | 苏州通富超威半导体有限公司 | Lithium ion battery cathode composite material and preparation method and application thereof |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104979533A (en) * | 2015-04-17 | 2015-10-14 | 重庆大学 | Graphene nano-belt wound germanium nanoparticle composite material preparation method |
| CN104979533B (en) * | 2015-04-17 | 2020-12-08 | 重庆大学 | Preparation method of graphene nanoribbon wound germanium nanoparticle composite material |
| CN107673307A (en) * | 2016-08-01 | 2018-02-09 | 福建新峰二维材料科技有限公司 | Germanium/graphene/titanium dioxide nanofiber composite material and preparation method thereof and battery |
| CN106099066A (en) * | 2016-08-09 | 2016-11-09 | 商丘师范学院 | A kind of germanium dioxide/graphene composite material and preparation method thereof |
| CN109599536A (en) * | 2017-09-30 | 2019-04-09 | 天津大学 | Germanium hydrogen/redox graphene/conductive black nano composite lithium ion cell negative electrode material and preparation method thereof |
| CN110707303A (en) * | 2019-10-15 | 2020-01-17 | 商丘师范学院 | Ionic liquid/germanium quantum dot composite material and preparation method and application thereof |
| CN110707303B (en) * | 2019-10-15 | 2022-06-28 | 商丘师范学院 | Ionic liquid/germanium quantum dot composite material and preparation method and application thereof |
| CN111640927A (en) * | 2020-06-17 | 2020-09-08 | 中国人民解放军国防科技大学 | Graphene-bridged polythiophene-coated germanium nanoparticle composite material and preparation method and application thereof |
| CN113991116A (en) * | 2021-10-22 | 2022-01-28 | 苏州通富超威半导体有限公司 | Lithium ion battery cathode composite material and preparation method and application thereof |
| CN113991116B (en) * | 2021-10-22 | 2023-06-30 | 苏州通富超威半导体有限公司 | Lithium ion battery negative electrode composite material and preparation method and application thereof |
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