CN106315665A - Method of preparing GeO2 submicron rod with high charge-discharge capacity - Google Patents
Method of preparing GeO2 submicron rod with high charge-discharge capacity Download PDFInfo
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- CN106315665A CN106315665A CN201610650177.5A CN201610650177A CN106315665A CN 106315665 A CN106315665 A CN 106315665A CN 201610650177 A CN201610650177 A CN 201610650177A CN 106315665 A CN106315665 A CN 106315665A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G17/00—Compounds of germanium
- C01G17/02—Germanium dioxide
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/10—Particle morphology extending in one dimension, e.g. needle-like
- C01P2004/16—Nanowires or nanorods, i.e. solid nanofibres with two nearly equal dimensions between 1-100 nanometer
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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Abstract
The invention relates to the technical field of lithium ion battery cathode materials, in particular to a method of preparing GeO2 submicron rod with high charge-discharge capacity. The method includes the steps that a Ca(NO3)2 water solution and GeO2 ammonia water solution are mixed to obtain a mixed solution; the mixed solution is added into a hydrothermal reaction kettle and reacts for 5-20 h at the temperature of 160-220 DEG C to obtain a calcium germinate submicron rod; the prepared calcium germinate submicron rod powder is added into concentrated nitric acid to be etched, and the etching time is 0.5-3 h; precipitate obtained after etching is centrifugally separated, the precipitate is calcined for 1-3 h in a muffle furnace at the temperature of 500-600 DEG C to obtain the GeO2 submicron rod. The prepared GeO2 submicron rod can be used as a lithium ion battery cathode material, has high charge-discharge capacity and has good cycle performance.
Description
Technical field
The invention belongs to inorganic energy storage material technical field, relate to lithium ion battery negative material, be specifically related to a kind of system
The GeO of standby high charge-discharge capacity2The method of sub-micrometer rod.
Background technology
In recent years, along with the continuous worsening of environment and the shortage of Fossil fuel, blowdown is lacked and the hybrid power of zero-emission
Automobile and pure electric automobile obtain wideling popularize of national governments, become the new-energy automobile first developed.And new-energy automobile
Key position be power supply, current optimal power supply is lithium ion battery, this is because it to have energy density high, power is close
Degree height, running voltage is high, has extended cycle life, the advantages such as environmental pollution is little, and self discharge is little.For meeting people's life requirement, new energy
The performance of source automobile, the most once charge stroke, it is necessary to improves further.Lithium ion battery is just proposed higher by this
Requirement.
Electrode is the core component of lithium ion battery, and electrode material decides the capacity of battery.The raising palpus of battery capacity
Start with from electrode material.At present, the graphite cathode material used by lithium ion battery, theoretical capacity only has 372 mAh/g, Er Qiecun
In certain safety issue.And the GeO of stable chemical performance2Negative material has relatively low operation voltage (0 ~ 0.4 V),
Higher theoretical capacity (1100 mAh/g), is suitable for substituting graphite.At present, relevant GeO2The research of negative material is in full generation
Boundary gradually rises.
Although GeO2There is lot of advantages, but its disadvantage existed is that change in volume is acute in charge and discharge process
Strong, thus affect the cycle performance of material.For this problem, currently mainly use and conductive material, such as agraphitic carbon, graphite
The way that alkene, CNT etc. are combined buffers GeO2Change in volume, and then improve its cycle performance.
Summary of the invention
It is an object of the invention to provide one and there is high charge-discharge capacity, and the GeO of good cycle2Lithium ion battery
Negative material, with and preparation method thereof.
For achieving the above object, the present invention technical scheme as follows: a kind of GeO preparing high charge-discharge capacity2Sub-micro
The method of rice rod, step is as follows:
(1), by Ca (NO3)2Aqueous solution and GeO2Ammonia spirit mix, obtain mixed liquor；
(2), above-mentioned mixed liquor is joined in hydrothermal reaction kettle, react 5 ~ 20 h at 160 ~ 220 DEG C, obtain germanic acid calcium sub-
Micron bar；
(3), by prepared germanic acid calcium sub-micrometer rod powder joining in concentrated nitric acid and perform etching, etch period is 0.5 ~ 3 h；
(4), centrifugation goes out the precipitate after etching, and calcines 1 ~ 3 little in Muffle furnace at 500 ~ 600 DEG C by precipitate
Time, obtain described GeO2Sub-micrometer rod.
Further, in step (1), Ca (NO3)2Aqueous solution and GeO2Ammonia spirit mixing time, Ca with Ge rubs
Your ratio is 1.1 ~ 1.2:1.
In step (3), concentrated nitric acid is more than 10:1 with the mass ratio of germanic acid calcium sub-micrometer rod powder.
Beneficial effect:
The present invention uses germanic acid calcium sub-micrometer rod as sacrificing template, uses concentrated nitric acid as template etching agent, utilizes sacrificial mold
Plate method is finally prepared for GeO2Sub-micrometer rod.Wherein, utilize the highly acid of concentrated nitric acid, dissolve the Ca in germanic acid calcium sub-micrometer rod
Composition, and its strong oxidizing property can preserve GeO2Composition, due to pattern memory effect, the GeO of final gained2Still remain Asia
Micron bar pattern.
GeO prepared by the present invention2Sub-micrometer rod, diameter 200 ~ 500 nm, length 2 ~ 10 μm, can as lithium from
Sub-cell negative electrode material uses, under the electric current density of 100 mA/g, and GeO2The reversible capacity first of sub-micrometer rod electrode is (i.e.
Charging capacity) it is 1050 ~ 1080 mAh/g, through 100 circulations, capability retention is 80% ~ 85%, and it shows relatively
High charge/discharge capacity, and there is good cycle performance.
Accompanying drawing explanation
Fig. 1 is the XRD figure of the germanium dioxide sub-micrometer rod of the embodiment of the present invention 1.
Fig. 2 is the scanning electron microscope diagram of the germanium dioxide sub-micrometer rod of the embodiment of the present invention 1.
Fig. 3 is that the discharge and recharge under the electric current density of 100 mA/g of the germanium dioxide sub-micrometer rod of the embodiment of the present invention 1 is bent
Line.
Detailed description of the invention
Embodiment 1
A kind of GeO preparing high charge-discharge capacity2The method of sub-micrometer rod, step is as follows:
1), by Ca (NO3)2It is dissolved in deionized water, forms 0.05 M solution 40 mL；By GeO2Powder adds 0.1 M of 10 mL
In ammonia spirit, it is completely dissolved；Make Ca (NO3)2Solution and GeO2In solution, the mol ratio of Ca Yu Ge is 1.1:1, and both are molten
Liquid mixes, magnetic agitation 10 min；
2), by the mixed liquor obtained transfer in 100 mL hydrothermal reaction kettles, add deionized water to reactor cumulative volume
80%, react 5 h at 160 DEG C, obtain germanic acid calcium sub-micrometer rod；
3), by prepared germanic acid calcium sub-micrometer rod powder joining in the concentrated nitric acid of 10 mL and perform etching, etch period is 0.5
H, wherein, concentrated nitric acid is 11:1 with the mass ratio of germanic acid calcium sub-micrometer rod powder；
4), by the precipitate centrifugation after etching, without deionized water or washing with alcohol, isolated precipitate is directly horse
Not stove is calcined 1 hour at 500 DEG C, i.e. obtain described GeO2Sub-micrometer rod.
As it is shown in figure 1, X-ray powder diffraction shows, obtained GeO2Sub-micrometer rod is the germanium dioxide of hexagonal phase, right
Answering JCPDS card to number (36-1463), free from admixture peak occurs, illustrates that product purity is higher.
As in figure 2 it is shown, scanning electron microscope (SEM) photograph display GeO2A diameter of 200 ~ 400 nm of sub-micrometer rod, a length of 2 ~ 8 μm.
Germanium dioxide sub-micrometer rod prepared by the present embodiment is used as lithium ion battery negative material, tests its electrochemistry
Performance.Concrete grammar is as follows: by germanium dioxide submicron and conductive agent (acetylene black) and bonding agent (PVDF) according to mass ratio
The ratio uniform mixing of 80:10:10.Agate mortar carefully grinds 20 minutes, N-Methyl pyrrolidone solution is added
In ground mixture, stir until mixture is uniform thickness paste, then slurry is coated with equably
On the copper sheet of a diameter of 14 mm, copper sheet is put into 80 DEG C dry 10 hours in air dry oven, i.e. makes electrode to be measured.With
Metal lithium sheet is that it is barrier film that the U.S. produces cell guard 2400,1 M LiPF to electrode (reference electrode)4EC/DMC solution
For electrolyte, vacuum glove box is assembled into 2032 type button cells.The LandBT2013A type using Wuhan indigo plant electricity to produce fills
Discharge instrument carries out charge-discharge performance test to battery.As it is shown on figure 3, under the electric current density of 100 mA/g, the present embodiment is made
Standby germanium dioxide nanometer rods respectively 1,10,30,100 times circulation after charging and discharging curve.Fig. 3 shows, 100 mA/g's
Under electric current density, germanium dioxide nanometer rods initial charge (the most reversible) capacity prepared by the present embodiment is 1065 mAh/g, far
Capacity (theoretical value 372 mAh/g) higher than the most commercial graphite cathode material.After 100 times circulate, this material reversible
Charging capacity still may be up to 853 mAh/g, and capability retention is 80 %.
Embodiment 2
A kind of GeO preparing high charge-discharge capacity2The method of sub-micrometer rod, step is as follows:
1), by Ca (NO3)2It is dissolved in deionized water, forms 0.15 M solution 40 mL；By GeO2Powder adds the 0.2 M ammonia of 6 mL
In aqueous solution, it is completely dissolved；Make Ca (NO3)2Solution and GeO2In solution, the mol ratio of Ca Yu Ge is 1.1:1, will both solution
Mixing, magnetic agitation 10 min；
2), by the mixed liquor obtained transfer in 100 mL hydrothermal reaction kettles, add deionized water to reactor cumulative volume
80%, react 8 h at 170 DEG C, obtain germanic acid calcium sub-micrometer rod；
3), by prepared germanic acid calcium sub-micrometer rod powder joining in the concentrated nitric acid of 12 mL and perform etching, etch period is 1 h,
Wherein, concentrated nitric acid is 12:1 with the mass ratio of germanic acid calcium sub-micrometer rod powder；
4), by the precipitate centrifugation after etching, without deionized water or washing with alcohol, isolated precipitate is directly horse
Not stove is calcined 2 hours at 500 DEG C, i.e. obtain described GeO2Sub-micrometer rod.
Germanium dioxide sub-micrometer rod prepared by the present embodiment is used as lithium ion battery negative material, tests its electrochemistry
Performance.Concrete grammar is with embodiment 1.The LandBT2013A type discharge and recharge instrument using Wuhan indigo plant electricity to produce carries out charge and discharge to battery
Electric performance test.Under the electric current density of 100 mA/g, germanium dioxide nanometer rods initial charge prepared by the present embodiment (
Inverse) capacity is 1050 mAh/g.After 100 times circulate, the reversible charging capacity of this material still may be up to 861 mAh/g, capacity
Conservation rate is 82 %.
Embodiment 3
A kind of GeO preparing high charge-discharge capacity2The method of sub-micrometer rod, step is as follows:
1), by Ca (NO3)2It is dissolved in deionized water, forms 0.4 M solution 40 mL；By GeO2Powder adds the 0.5 M ammonia of 5 mL
In aqueous solution, it is completely dissolved；Make Ca (NO3)2Solution and GeO2In solution, the mol ratio of Ca Yu Ge is 1.15:1, will both solution
Mixing, magnetic agitation 10 min；
2), by the mixed liquor obtained transfer in 100 mL hydrothermal reaction kettles, add deionized water to reactor cumulative volume
80%, react 10 h at 180 DEG C, obtain germanic acid calcium sub-micrometer rod；
3), by prepared germanic acid calcium sub-micrometer rod powder joining in the concentrated nitric acid of 15 mL and perform etching, etch period is 3 h,
Wherein, concentrated nitric acid is 13:1 with the mass ratio of germanic acid calcium sub-micrometer rod powder；
4), by the precipitate centrifugation after etching, without deionized water or washing with alcohol, isolated precipitate is directly horse
Not stove is calcined 1.5 hours at 550 DEG C, i.e. obtain described GeO2Sub-micrometer rod.
Germanium dioxide sub-micrometer rod prepared by the present embodiment is used as lithium ion battery negative material, tests its electrochemistry
Performance.Concrete grammar is with embodiment 1.The LandBT2013A type discharge and recharge instrument using Wuhan indigo plant electricity to produce carries out charge and discharge to battery
Electric performance test.Under the electric current density of 100 mA/g, germanium dioxide nanometer rods initial charge prepared by the present embodiment (
Inverse) capacity is 1078 mAh/g.After 100 times circulate, the reversible charging capacity of this material still may be up to 891 mAh/g, capacity
Conservation rate is 83 %.
Embodiment 4
A kind of GeO preparing high charge-discharge capacity2The method of sub-micrometer rod, step is as follows:
1), by Ca (NO3)2It is dissolved in deionized water, forms 0.6 M solution 40 mL；By GeO2Powder adds the 0.7 M ammonia of 6 mL
In aqueous solution, it is completely dissolved；Make Ca (NO3)2Solution and GeO2In solution, the mol ratio of Ca Yu Ge is 1.1:1, will both solution
Mixing, magnetic agitation 10 min；
2), by the mixed liquor obtained transfer in 100 mL hydrothermal reaction kettles, add deionized water to reactor cumulative volume
80%, react 20 h at 190 DEG C, obtain germanic acid calcium sub-micrometer rod；
3), by prepared germanic acid calcium sub-micrometer rod powder joining in the concentrated nitric acid of 18 mL and perform etching, etch period is 2h,
Wherein, concentrated nitric acid is 14:1 with the mass ratio of germanic acid calcium sub-micrometer rod powder；
4), by the precipitate centrifugation after etching, without deionized water or washing with alcohol, isolated precipitate is directly horse
Not stove is calcined 2 hours at 600 DEG C, i.e. obtain described GeO2Sub-micrometer rod.
Germanium dioxide sub-micrometer rod prepared by the present embodiment is used as lithium ion battery negative material, tests its electrochemistry
Performance.Concrete grammar is with embodiment 1.The LandBT2013A type discharge and recharge instrument using Wuhan indigo plant electricity to produce carries out charge and discharge to battery
Electric performance test.Under the electric current density of 100 mA/g, germanium dioxide nanometer rods initial charge prepared by the present embodiment (
Inverse) capacity is 1075 mAh/g.After 100 times circulate, the reversible charging capacity of this material still may be up to 903 mAh/g, capacity
Conservation rate is 84 %.
Embodiment 5
A kind of GeO preparing high charge-discharge capacity2The method of sub-micrometer rod, step is as follows:
1), by Ca (NO3)2It is dissolved in deionized water, forms 1 M solution 40 mL；By GeO2Powder adds the 0.9 M ammonia of 8 mL
In solution, it is completely dissolved；Make Ca (NO3)2Solution and GeO2In solution, the mol ratio of Ca Yu Ge is 1.2:1, is mixed by both solution
Close, magnetic agitation 10 min；
2), by the mixed liquor obtained transfer in 100 mL hydrothermal reaction kettles, add deionized water to reactor cumulative volume
80%, react 7 h at 220 DEG C, obtain germanic acid calcium sub-micrometer rod；
3), by prepared germanic acid calcium sub-micrometer rod powder joining in the concentrated nitric acid of 20 mL and perform etching, etch period is 1h,
Wherein, concentrated nitric acid is 15:1 with the mass ratio of germanic acid calcium sub-micrometer rod powder；
4), by the precipitate centrifugation after etching, without deionized water or washing with alcohol, isolated precipitate is directly horse
Not stove is calcined 3 hours at 500 DEG C, i.e. obtain described GeO2Sub-micrometer rod.
Germanium dioxide sub-micrometer rod prepared by the present embodiment is used as lithium ion battery negative material, tests its electrochemistry
Performance.Concrete grammar is with embodiment 1.The LandBT2013A type discharge and recharge instrument using Wuhan indigo plant electricity to produce carries out charge and discharge to battery
Electric performance test.Under the electric current density of 100 mA/g, germanium dioxide nanometer rods initial charge prepared by the present embodiment (
Inverse) capacity is 1080 mAh/g.After 100 times circulate, the reversible charging capacity of this material still may be up to 920 mAh/g, capacity
Conservation rate is 85 %.
Claims (3)
1. the GeO preparing high charge-discharge capacity2The method of sub-micrometer rod, it is characterised in that: step is as follows:
(1), by Ca (NO3)2Aqueous solution and GeO2Ammonia spirit mix, obtain mixed liquor；
(2), above-mentioned mixed liquor is joined in hydrothermal reaction kettle, react 5 ~ 20 h at 160 ~ 220 DEG C, obtain germanic acid calcium sub-
Micron bar；
(3), by prepared germanic acid calcium sub-micrometer rod powder joining in concentrated nitric acid and perform etching, etch period is 0.5 ~ 3 h；
(4), centrifugation goes out the precipitate after etching, and calcines 1 ~ 3 little in Muffle furnace at 500 ~ 600 DEG C by precipitate
Time, obtain described GeO2Sub-micrometer rod.
A kind of GeO preparing high charge-discharge capacity2The method of sub-micrometer rod, it is characterised in that: step
Suddenly in (1), Ca (NO3)2Aqueous solution and GeO2Ammonia spirit mixing time, the mol ratio of Ca Yu Ge is 1.1 ~ 1.2:1.
A kind of GeO preparing high charge-discharge capacity2The method of sub-micrometer rod, it is characterised in that: step
Suddenly, in (3), concentrated nitric acid is more than 10:1 with the mass ratio of germanic acid calcium sub-micrometer rod powder.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109037652A (en) * | 2018-08-16 | 2018-12-18 | 福州大学 | A kind of preparation method and application of nitrogen-doped carbon cladding graduation germanium junction structure |
| CN109248677A (en) * | 2018-06-06 | 2019-01-22 | 青岛农业大学 | Germanium dioxide nano enzyme and its Pesticides Testing application |
| CN110790304A (en) * | 2019-11-13 | 2020-02-14 | 福州大学 | Preparation of germanium dioxide/nitrogen-doped carbon composite material with sea urchin-shaped structure and application of composite material in lithium ion battery |
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| JPS61136998A (en) * | 1984-12-06 | 1986-06-24 | Alps Electric Co Ltd | Germanium oxide whisker and its manufacture |
| CN102534268A (en) * | 2010-12-28 | 2012-07-04 | 北京有色金属研究总院 | Production method of high-purity germanium dioxide |
| CN102774877A (en) * | 2012-08-03 | 2012-11-14 | 云南驰宏锌锗股份有限公司 | Novel process for preparing germanium dioxide (GeO2) |
-
2016
- 2016-08-09 CN CN201610650177.5A patent/CN106315665B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61136998A (en) * | 1984-12-06 | 1986-06-24 | Alps Electric Co Ltd | Germanium oxide whisker and its manufacture |
| CN102534268A (en) * | 2010-12-28 | 2012-07-04 | 北京有色金属研究总院 | Production method of high-purity germanium dioxide |
| CN102774877A (en) * | 2012-08-03 | 2012-11-14 | 云南驰宏锌锗股份有限公司 | Novel process for preparing germanium dioxide (GeO2) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109248677A (en) * | 2018-06-06 | 2019-01-22 | 青岛农业大学 | Germanium dioxide nano enzyme and its Pesticides Testing application |
| CN109248677B (en) * | 2018-06-06 | 2021-06-04 | 青岛农业大学 | Germanium dioxide nanoenzyme and pesticide detection application thereof |
| CN109037652A (en) * | 2018-08-16 | 2018-12-18 | 福州大学 | A kind of preparation method and application of nitrogen-doped carbon cladding graduation germanium junction structure |
| CN109037652B (en) * | 2018-08-16 | 2021-04-27 | 福州大学 | Preparation method and application of nitrogen-doped carbon-coated graded germanium structure |
| CN110790304A (en) * | 2019-11-13 | 2020-02-14 | 福州大学 | Preparation of germanium dioxide/nitrogen-doped carbon composite material with sea urchin-shaped structure and application of composite material in lithium ion battery |
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