CN104617256B - Nano zine oxide graphite graphene composite material and its preparation method and application - Google Patents
Nano zine oxide graphite graphene composite material and its preparation method and application Download PDFInfo
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- CN104617256B CN104617256B CN201510031315.7A CN201510031315A CN104617256B CN 104617256 B CN104617256 B CN 104617256B CN 201510031315 A CN201510031315 A CN 201510031315A CN 104617256 B CN104617256 B CN 104617256B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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- H01—ELECTRIC ELEMENTS
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- 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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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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- H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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Abstract
The invention discloses nano zine oxide graphite graphene composite material and its preparation method and application.The nano zine oxide graphite graphene composite material, described composite includes core and clad, and described core is made up of graphite and graphene, and described clad is nano zine oxide and the uniform complex of amorphous carbon.It comprises the steps：Soluble zinc salt and organic high molecular polymer are dissolved in alcohol organic solvent, it is well mixed to obtain solution A；The mixture of graphite and graphene oxide is added in Aqueous Solutions of Polyethylene Glycol, ultrasonic disperse uniformly obtains suspension B；Solution A is mixed with suspension B, polyvinylpyrrolidone is added, after stirring, then the mixture of ammoniacal liquor and ethanol is added dropwise, obtains sol-gel system C；Dry, roasting heat treatment, you can.The composite material preparation process of the present invention is simple, can effectively alleviate Volume Changes caused during discharge and recharge, and cycle performance is preferable.
Description
Technical field
The present invention relates to nano zine oxide-graphite-graphene composite material and its preparation method and application.
Background technology
Lithium ion battery is applied successfully to various portable due to its higher energy density and longer service life
Formula electronic equipment, such as mobile phone, portable computer.Industrialization lithium ion battery is mainly used as negative pole material using graphite at present
Material, and the theoretical capacity of graphite is only 370mAh/g, this promotes scientific research personnel to look for the material with higher theoretical capacity
To substitute or doped graphite is as negative material, to expect to obtain the lithium ion battery with higher storage capacity.
Theoretical capacity when zinc oxide (ZnO) is as lithium ion battery negative material is 978mAh/g.Block ZnO is used as
During lithium ion battery negative material, electron conductivity is low, and Volume Changes are big in charge and discharge process, and electrical contact loss is big, electrochemistry
Poor-performing, preferable charge/discharge capacity is not reached.
Graphene has good electricity, optically and thermally mechanics, property.Preferable single-layer graphene has the ratio of super large
Surface area (2630m2/ g), it is the energy storage material of great potential.Graphene has good electric conductivity, the movement velocity of its electronics
The 1/300 of the light velocity is reached, considerably beyond movement velocity of the electronics in general conductor.Graphene has good printing opacity
Property, it is the potential substitute products of traditional ito film.Graphene has good thermal property, is surveyed using based on micro- Raman spectroscopy
The thermal conductivity for measuring graphene is 3080~5150W/mK.
It is existing oxidation Zinc-graphite com- posite as negative electrode of lithium ion battery in use, in charge and discharge cycles process
In, volume is expanded and shunk, and causes die break, and structural breakdown causes the destruction of electrode, reduces the circulation of electrode
Life-span, and it causes initial irreversible capacity to increase in de- slotting lithium reaction easy " reunion ", ultimately results in capacity reduction.
The content of the invention
Existing graphite cathode material charge/discharge capacity is low, volume is easily expanded present invention aim to overcoming and
Shrink, cause die break, structural breakdown causes the destruction of electrode, reduce the cycle life of electrode, and it is anti-in de- slotting lithium
Seasonable easily " reunions " cause the defect of capacity reduction there is provided a kind of nano zine oxide-graphite-graphene composite material and its
Preparation method and application.Nano zine oxide-graphite-graphene composite material preparation technology of the present invention is simple, can be effectively
Alleviate Volume Changes caused during discharge and recharge, suppress " reunion " phenomenon in de- slotting lithium reaction, material electrodes can be avoided
Capacity attenuation is too fast, reduces initial irreversible capacity so that the capacity of nano zine oxide-graphite-graphene composite material is long-range
In the theoretical capacity of common carbon material, and cycle performance is preferable.
The present invention solves above-mentioned technical problem using following technical scheme：
The invention provides a kind of nano zine oxide-graphite-graphene composite material, described composite includes core
And clad, described core is made up of graphite and graphene, and described clad is equal for nano zine oxide and amorphous carbon
Even complex.
Wherein, the particle diameter of described graphite is preferably 0.1~5 μm, is more preferably 0.5~1 μm.Described graphite is preferable
One or more of the ground in natural spherical plumbago, natural flake graphite and aquadag.Described graphite accounts for described answer
The weight/mass percentage composition of condensation material is preferably 65~85%.
Wherein, described graphene accounts for the weight/mass percentage composition of described composite and is preferably 1~5%.
Wherein, described nano zine oxide accounts for the weight/mass percentage composition of described composite and is preferably 5%~25%.
Wherein, described amorphous carbon accounts for the weight/mass percentage composition of described composite and is preferably 5%~10%.
Present invention also offers the preparation method of above-mentioned nano zine oxide-graphite-graphene composite material, it includes following
Step：
(1) soluble zinc salt and organic high molecular polymer are dissolved in alcohol organic solvent, it is well mixed to obtain molten
Liquid A；
(2) mixture of graphite and graphene oxide is added in Aqueous Solutions of Polyethylene Glycol, ultrasonic disperse is uniformly obtained
Suspension B；
(3) solution A is mixed with suspension B, adds polyvinylpyrrolidone, after stirring, then ammoniacal liquor and second is added dropwise
The mixture of alcohol, obtains sol-gel system C；
(4) described sol-gel system C is dried, obtains presoma D；
(5) described presoma D is calcined heat treatment in protective gas, you can.
Wherein, in step (1), described alcohol organic solvent be preferably one kind in methanol, ethanol and isopropanol or
It is a variety of.
Wherein, described soluble zinc salt is generally water-soluble zinc salt commonly used in the art, and the present invention is preferably
Four ammino zinc complexes, the further preferred ammino zinc (Zn (NH of sulfuric acid four3)4SO4), the ammino zinc (Zn (NH of carbonic acid four3)4CO3) and
Ammino zinc (Zn (the NH of dichloride four3)4Cl2) in one or more.
Wherein, described organic high molecular polymer is as presoma, preferably phenolic resin, furane resins, coal
One or more in pitch and asphalt.
Wherein, the mass ratio of described soluble zinc salt and described organic high molecular polymer is preferably 1：(0.5~
2)。
Wherein, described graphite can be various graphite commonly used in the art, preferably natural spherical plumbago, colloid
One or more in graphite and natural flake graphite.The particle diameter of described graphite is preferably 0.1~5 μm, is more preferably 0.5
~1 μm.
Wherein, described graphene oxide can be graphene oxide commonly used in the art, generally refer to graphite
(Graphite) graphite oxide obtained after the oxidation of HUMMMERS methods, then it is scattered with ultrasonic wave so that oxidized graphite flake
Layer is peeled off and produced.
Wherein, the mass ratio of described graphite and graphene oxide is preferably (20~100)：1.
Wherein, the mass ratio of described graphite and described soluble zinc salt is preferably (3~15)：1.
Wherein, the one or more in described polyethylene glycol preferred PEG-4000, PEG-6000 and PEG-8000；It is described
The mass percent concentration of Aqueous Solutions of Polyethylene Glycol be preferably 5~20%.
Wherein, the weight average molecular weight of described polyvinylpyrrolidone is preferably 8000~10000.
Wherein, the mass ratio of described polyvinylpyrrolidone and described soluble zinc salt is preferably (1~20)：1.
Wherein, the volume ratio of described ammoniacal liquor and ethanol is preferably 1：(10~100).
Wherein, described drying is preferably comprised dries and dries for the second time for the first time；The temperature that described first time is dried
Preferably 80~90 DEG C of degree, the time that described first time is dried is preferably 2~3 hours；Second described of drying
Temperature is preferably 180~200 DEG C, and the time of second described of drying is preferably 4~6 hours.
Wherein, described protective gas is preferably nitrogen or inert gas, and described inert gas is helium, neon
One or more in gas, argon gas, Krypton and xenon.
Wherein, the temperature of described roasting heat treatment is preferably 1200~2000 DEG C, described roasting heat treatment when
Between preferably 5~10 hours.
Present invention also offers above-mentioned nano zine oxide-graphite-graphene composite material in negative electrode of lithium ion battery
Using.
On the basis of common sense in the field is met, above-mentioned each optimum condition can be combined, and produce each preferable reality of the present invention
Example.
Agents useful for same and raw material of the present invention are commercially available.
The positive effect of the present invention is：
(1) present invention uses organic solvent system, rather than general water solution system, makes graphite, graphene, zinc salt and has
Machine high molecular polymer forms a kind of uniform collosol-gelatum system, is not precipitated from beginning to end in material preparation process,
So as to finally give the composite with cladding Rotating fields, a kind of similar composite of core shell structure.
(2) in the composite, zinc oxide high uniformity in amorphous carbon material disperses, and oxide particle is difficult group
Poly-, material structure is stable.
(3) nano zine oxide-graphite-graphene composite material preparation technology of the invention is simple, can effectively alleviate
Caused Volume Changes during discharge and recharge, suppress " reunion " phenomenon in de- slotting lithium reaction, can avoid material electrodes capacity
Decay is too fast, reduces initial irreversible capacity so that the capacity of nano zine oxide-graphite-graphene composite material is much larger than general
The theoretical capacity of logical carbon material, and cycle performance is preferable.
Brief description of the drawings
Fig. 1 is the SEM photograph of nano zine oxide-graphite-graphene composite material produced by the present invention.
Fig. 2 is that nano zine oxide-graphite-graphene composite material made from embodiment 1 is used as negative electrode of lithium ion battery material
The cycle performance curve of material.
Embodiment
The present invention is further illustrated below by the mode of embodiment, but does not therefore limit the present invention to described reality
Apply among a scope.The experimental method of unreceipted actual conditions in the following example, conventionally and condition, or according to business
Product specification is selected.
Graphene oxide in following embodiments is made by HUMMMERS oxidizing process, particular reference Fast and
Facile Preparation of Graphene Oxide and Reduced Graphene Oxide
Nanoplatelets, Chem.Mater., volume 21, page 3514~3520 and《Graphene oxide reduction prepares graphene
Technique study》, Chinese material science and technology and equipment, the 4th phase in 2012, page 36~39.
Embodiment 1
Weigh the ammino zinc (Zn (NH of 10g sulfuric acid four3)4SO4) and 10g asphalt be dissolved in 300ml ethanol and stir
Obtain solution A.100g natural spherical plumbagos (particle diameter is 0.5~1 μm) and 2g graphene oxides are added to mass percent dense
Spend in polyethylene glycol (PEG-4000) aqueous solution for 10%, ultrasonic disperse 30min obtains suspension B.By solution A with suspending
After liquid B mixing, 50g polyvinylpyrrolidones (weight average molecular weight is 8000~10000) are added, after stirring, then ammonia are added dropwise
(volume ratio of ammoniacal liquor and ethanol is 1 to water with ethanol:50) mixture 300mL, obtains sol-gel system C.By above-mentioned colloidal sol
Gel rubber system C is dried 3 hours at 80 DEG C, and 200 DEG C of dryings are then warming up to again and obtain presoma D within 4 hours；Presoma D is existed
Roasting heat treatment 9 hours under the conditions of 1500 DEG C in nitrogen, you can obtain nano zine oxide-graphite-graphene composite material.
In the composite sample, content of graphite is 70wt%, and graphene content is 2wt%, and nano oxidized Zn content is
18wt%, agraphitic carbon content is 10wt%.
Which part sample is taken to be scanned electron micrograph, gained SEM photograph is shown in Fig. 1.Can from Fig. 1
Go out, nano zine oxide-graphite-graphene composite material particle maintains spherical appearance characteristics, the surface ratio of composite
Raw graphite ball is smooth, illustrates to have coated one layer of shell on raw graphite ball, the table of tiny particles coat in graphite matrix
Face, constitutes relatively uniform shell, and core-shell structure copolymer is well combined, and is not departed from.
Embodiment 2
Weigh the ammino zinc (Zn (NH of 10g carbonic acid four3)4CO3) and 20g coal tar pitch be dissolved in 400ml methanol and stir
To solution A.It is 5% that 80g aquadags (particle diameter is 0.5~1 μm) and 1g graphene oxides are added into mass percent concentration
Polyethylene glycol (PEG-8000) aqueous solution in, ultrasonic disperse 50min obtains suspension B.Solution A is mixed with suspension B
Afterwards, 60g polyvinylpyrrolidones (weight average molecular weight is 8000~10000) are added, after stirring, then ammoniacal liquor and ethanol are added dropwise
(volume ratio of ammoniacal liquor and ethanol is 1:20) mixture 500mL, obtains sol-gel system C.By above-mentioned sol-gel system C
Dried 3 hours at 90 DEG C, 180 DEG C of dryings are then warming up to again and obtain presoma D within 6 hours；By presoma D 2000 in nitrogen
Roasting heat treatment 6 hours under the conditions of DEG C, you can obtain nano zine oxide-graphite-graphene composite material.
In the composite sample, content of graphite is 64wt%, and graphene content is 3wt%, and nano oxidized Zn content is
23wt%, agraphitic carbon content is 10wt%.
The SEM photograph be the same as Example 1 of nano zine oxide-graphite-graphene composite material made from the present embodiment.
Embodiment 3
Weigh the ammino zinc (Zn (NH of 10g dichlorides four3)4Cl2) and 5g phenolic resin be dissolved in 200ml isopropanols stir
Uniformly obtain solution A.50g natural spherical plumbagos (particle diameter is 0.5~1 μm) and 2g graphene oxides are added to mass percent
Concentration is in 20% polyethylene glycol (PEG-6000) aqueous solution, ultrasonic disperse 40min obtains suspension B.By solution A with hanging
After supernatant liquid B mixing, 50g polyvinylpyrrolidones (weight average molecular weight is 8000~10000) are added, after stirring, then are added dropwise
(volume ratio of ammoniacal liquor and ethanol is 1 to ammoniacal liquor with ethanol:10) mixture 200mL, obtains sol-gel system C.Will be above-mentioned molten
Sol-gel system C is dried 3 hours at 90 DEG C, and 190 DEG C of dryings are then warming up to again and obtain presoma D within 5 hours；By presoma D
Roasting heat treatment 10 hours under the conditions of 1200 DEG C in helium, you can obtain nano zine oxide-graphite-graphene composite material.
In the composite sample, content of graphite is 67wt%, and graphene content is 5wt%, and nano oxidized Zn content is
20wt%, agraphitic carbon content is 8wt%.
The SEM photograph be the same as Example 1 of nano zine oxide-graphite-graphene composite material made from the present embodiment.
The composite produced by the present invention of effect example 1 as lithium ion battery negative material electric performance test (half
Battery testing method)
Half-cell method of testing of the invention used is：Make 2430 type batteries, it is composite sample, poly- inclined containing 6~7%
The 1-METHYLPYRROLIDONE of PVF and 2% conductive black are well mixed, be applied on copper foil, the pole piece coated is put into temperature
It is standby to be dried in vacuo 4 hours in 110 DEG C of vacuum drying chambers.Simulated battery is assemblied in the German Braun glove box of applying argon gas
Carry out, electrolyte is 1M LiPF6+EC: EMC: DMC=1: 1: 1 (volume ratio), metal lithium sheet is that, to electrode, chemical property is surveyed
Examination is carried out on U.S. ArbinBT2000 type cell testers, discharge and recharge system：Current potential is limited to 0-1.5V and carries out discharge charge
Electrical testing, i.e. use charging current 0.5mA/cm2It is that 0.01V charges to battery to keep voltage simultaneously, then uses charging current
0.02mA/cm2It is that 0.01V continues to charge to keep voltage simultaneously.Use discharge current 0.5mA/cm2Discharge battery to voltage is 1.5V.
Test result is shown in Table 1.
Table 1
Can be seen that composite produced by the present invention from data above, discharge capacity is up to more than 535mAh/g first,
And first charge-discharge efficiency is higher, capability retention is more than 90% after circulating 500 weeks.And the composite of the present invention can
Effectively to alleviate Volume Changes caused during discharge and recharge, suppress " reunion " phenomenon in de- slotting lithium reaction, in circulation 500
Electrode expansion rate is respectively less than 130% after week, is conducive to suppressing lithium-ion battery system generation ballooning, the security performance of battery
It is good, it is significantly better than graphite negative material of lithium ion battery of the prior art.
Electric performance test (the full battery testing of the graphite negative material of lithium ion battery produced by the present invention of effect example 2
Method)
Full battery testing method is used in of the invention：Negative pole, cobalt acid lithium are made with composite made from the embodiment of the present invention 1
Make positive pole, 1M-LiPF6EC: EMC: DMC=1: 1: 1 (volume ratio) solution makees electrolyte assembling and helps battery, tests 1C charge and discharges
500 weeks capability retentions are more than 90.0%, as shown in Figure 2.
Claims (9)
1. a kind of preparation method of nano zine oxide-graphite-graphene composite material, it comprises the steps：
(1) soluble zinc salt and organic high molecular polymer are dissolved in alcohol organic solvent, it is well mixed to obtain solution A；
(2) mixture of graphite and graphene oxide is added in Aqueous Solutions of Polyethylene Glycol, ultrasonic disperse is uniformly suspended
Liquid B；
(3) solution A is mixed with suspension B, adds polyvinylpyrrolidone, after stirring, then ammoniacal liquor and ethanol is added dropwise
Mixture, obtains sol-gel system C；
(4) described sol-gel system C is dried, obtains presoma D；
(5) described presoma D is calcined heat treatment in protective gas, you can；
Described composite includes core and clad, and described core is made up of graphite and graphene, described clad
For nano zine oxide and the uniform complex of amorphous carbon；The particle diameter of described graphite is 0.1~5 μm；Described graphite is selected from
One or more in natural spherical plumbago, natural flake graphite and aquadag；Described graphite accounts for described composite
Weight/mass percentage composition be 65~85%；The weight/mass percentage composition that described graphene accounts for described composite is 1~5%；
The weight/mass percentage composition that described nano zine oxide accounts for described composite is 5%~25%；Described amorphous carbon accounts for institute
The weight/mass percentage composition for the composite stated is 5%~10%.
2. preparation method as claimed in claim 1, it is characterised in that the particle diameter of described graphite is 0.5~1 μm.
3. preparation method as claimed in claim 1, it is characterised in that in step (1), described alcohol organic solvent is first
One or more in alcohol, ethanol and isopropanol；
Described soluble zinc salt is four ammino zinc complexes.
4. preparation method as claimed in claim 3, it is characterised in that described soluble zinc salt is the ammino zinc of sulfuric acid four, carbon
One or more in sour four ammino zinc and the ammino zinc of dichloride four.
5. preparation method as claimed in claim 1, it is characterised in that described organic high molecular polymer be phenolic resin,
One or more in furane resins, coal tar pitch and asphalt；
The mass ratio of described soluble zinc salt and described organic high molecular polymer is 1：(0.5~2)；
Described graphite is the one or more in natural spherical plumbago, aquadag and natural flake graphite；
Described graphite and the mass ratio of graphene oxide are (20~100)：1；
The mass ratio of described graphite and described soluble zinc salt is (3~15)：1.
6. preparation method as claimed in claim 1, it is characterised in that described polyethylene glycol is PEG-4000, PEG-6000
With the one or more in PEG-8000；The mass percent concentration of described Aqueous Solutions of Polyethylene Glycol is 5~20%；
The weight average molecular weight of described polyvinylpyrrolidone is 8000~10000；
The mass ratio of described polyvinylpyrrolidone and described soluble zinc salt is (1~20)：1；
Described ammoniacal liquor and the volume ratio of ethanol are 1：(10~100).
7. preparation method as claimed in claim 1, it is characterised in that described drying includes drying for the first time and second is dry
It is dry；The temperature that described first time is dried is 80~90 DEG C, and the time that described first time is dried is 2~3 hours；Described
The temperature of redrying is 180~200 DEG C, and the time of second described of drying is 4~6 hours.
8. preparation method as claimed in claim 1, it is characterised in that described protective gas is nitrogen or inert gas,
Described inert gas is the one or more in helium, neon, argon gas, Krypton and xenon.
9. preparation method as claimed in claim 1, it is characterised in that the temperature of described roasting heat treatment is 1200~2000
DEG C, the time of described roasting heat treatment is 5~10 hours.
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| CN105390676B (en) * | 2015-11-02 | 2018-06-15 | 北京师范大学 | A kind of fast preparation method of the graphene-based metal of sandwich structure or metal oxide |
| CN106442642B (en) * | 2016-08-30 | 2019-05-14 | 安徽师范大学 | A kind of preparation method of zinc oxide/graphene composite material, resistor-type gas sensor |
| CN109037643B (en) * | 2018-08-07 | 2020-10-20 | 内蒙古三信实业有限公司 | High-capacity high-compaction graphite composite material and preparation method thereof |
| CN109037645B (en) * | 2018-08-09 | 2021-07-20 | 哈尔滨工业大学 | Method for preparing metal oxide @ chlorine-doped graphene lithium ion battery anode material in one step |
| CN110931722B (en) * | 2019-10-14 | 2021-04-09 | 桂林理工大学 | Preparation method and application of camellia oleifera shell carbon/zinc oxide composite material |
| CN112768678B (en) * | 2019-11-05 | 2024-09-17 | 贝特瑞新材料集团股份有限公司 | Negative electrode material, preparation method thereof and lithium ion battery |
| CN111943254B (en) * | 2020-08-21 | 2021-05-28 | 电子科技大学 | Uniformly dispersed zinc oxide-multilayer graphene composite material and preparation method thereof |
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| CN101425580A (en) * | 2007-10-29 | 2009-05-06 | 比亚迪股份有限公司 | Negative electrode active substance of lithium ionic cell and preparing method thereof, negative electrode and cell |
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