CN109950486A - A kind of multistage composite metal oxide functional is ceramic and its applies - Google Patents
A kind of multistage composite metal oxide functional is ceramic and its applies Download PDFInfo
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Abstract
The present invention provides a kind of multistage composite metal oxide functional ceramics and its application, it is related to a kind of multistage composite metal oxide materials, it include: tubulose carbon skeleton and the metal composite oxide for being grown on tubulose carbon skeleton surface, the metal composite oxide includes the composite construction of ferriferous oxide and corronil.
Description
Technical field
The invention belongs to ceramic technology fields, and in particular to a kind of skeleton surface graft growth multistage composite metal oxide
Function ceramics and its preparation method and application.
Background technique
The energy is most important factor during human development, makes a general survey of the world today, and green energy resource replaces petroleum with electric energy
And natural gas, and the key of Development of EV is that battery.Since the reserves limitation of lithium cannot be largely used in automobile, sodium
Battery reserves are big, therefore are most promising battery materials.Metal oxide is also the heat of sodium-ion battery high-capacity cathode material
Point, the problem of mainly facing volume expansion, capacity attenuation, in order to overcome these problems, can by with carbon is compound, preparation electricity
The methods of chemical activity/nonactive composite material, synthesis special appearance nano material inhibit the volume expansion of material, improve material
Conductivity, and then realize the height ratio capacity of alloy materials, stablize circulation and excellent high rate performance.As most stable of
Iron oxide, bloodstone (α-Fe2O3) 1007 mAh/g are up to due to its capacity, it is non-toxic, it is inexpensive and rich cause
Special attention.And copper oxide research is more, performance is stable but charge/discharge capacity is not high.
Summary of the invention
In view of the above-mentioned problems, the purpose of the present invention is to provide a kind of oxidations of the multistage composite metal of electrochemical performance
Object material and its preparation method and application.
In a first aspect, the present invention provides a kind of multistage composite metal oxide materials comprising: tubulose carbon skeleton and
It is grown on the metal composite oxide on tubulose carbon skeleton surface, the metal composite oxide includes ferriferous oxide and cupro-nickel
Alloy.
According to the present invention, skeleton is made with carbon, more monocrystalline metal oxide faces can be exposed, to improve electrochemistry
Energy；Metal composite oxide includes ferriferous oxide and cupro-nickel compound, and wherein ferriferous oxide charge/discharge capacity is high, and nickel is conducive to mention
Battery capacity can be improved in stability when high circulation performance and high rate charge-discharge, copper.It is compound to carry out multiphase, each material can be combined
Material feature obtains better chemical property.Multistage composite metal oxide materials of the invention are as sodium-ion battery cathode
Material has broad prospects since it has both the capacity of metal oxide greatly and the cheap feature of raw material, and by its with consolidate
Fixed skeleton structure is joined together, then can further play stable structure, so that stable circulation.Therefore this kind is in multistage composite
Metal oxide materials can make up defect of the metal oxide as negative electrode material, be expected to the cathode material as sodium-ion battery
Material.
Preferably, the length of the tubulose carbon skeleton be 0.1~0.8 μm, caliber be 50~100nm, pipe thickness be 5~
50nm。
Preferably, the ferriferous oxide is Fe23.33O32, the copper-nickel compound is Cu0.81Ni0.19。
Preferably, the molar ratio of ferriferous oxide and corronil is 5:1~1:5.
Preferably, the metal composite oxide is in granular form, it is preferable that partial size is 30~500nm.
Preferably, the mass ratio of tubulose carbon skeleton and metal composite oxide is 1:5~1:20.
Second aspect, the present invention provide the preparation method of above-mentioned multistage composite metal oxide materials, comprising the following steps:
(1) organic carbon source is pyrolyzed, obtains product A；
(2) product A is uniformly mixed with copper source and source of iron, is pyrolyzed at 500~700 DEG C, obtains product B；
(3) product B is uniformly mixed with nickel source, is pyrolyzed at 500~700 DEG C, obtains product C；
(4) product C is pyrolyzed at 200~300 DEG C, obtains the composition metal oxidation that carbon makees skeletal support growth metal oxide
Object.
According to the present invention, it prepares carbon and makees skeleton, to expose more monocrystalline metal oxide faces, keep its structural support raw
Long metal oxide metal composite oxide improves the chemical property of battery as electrode material.The preparation method is simply easy
Operation, is not added with any organic matter, low in cost, environmentally friendly, is expected to realize industrialized production.
Preferably, the organic carbon source is selected from least one of urea, ethylenediamine tetra-acetic acid, citric acid.
Preferably, pyrolysis temperature is 300~600 DEG C in step (1), pyrolysis time is 1min~3h.
Preferably, product A is uniformly mixed with copper source and source of iron by the following method in step (2): by product A and copper
Source and source of iron mixed grinding, are then completely dissolved in water and obtain solution, acquired solution is freeze-dried.
Preferably, product A is (1~2): (3~4): (5~10) with the mass ratio of copper source and source of iron in step (2).
Preferably, being warming up to 500~700 DEG C in step (2) with 5~10 DEG C/min and keeping the temperature 0.1~3 hour.
Preferably, product B is uniformly mixed with nickel source by the following method in step (3): product B is mixed with nickel source
Grinding, is then completely dissolved in water and obtains solution, and acquired solution is dry.
Preferably, the mass ratio of product B and nickel source is 10:1~6:1 in step (3).
Preferably, being warming up to 500~700 DEG C in step (3) with 5~10 DEG C/min and keeping the temperature 0.1~3 hour.
Preferably, copper source is mantoquita, it preferably is selected from least one of copper acetate, cupric oxalate, copper nitrate；The source of iron
For molysite, it preferably is selected from least one of ferric nitrate, ammonium ferric oxalate, iron chloride；The nickel source is nickel salt, preferably is selected from nitric acid
At least one of nickel, nickel acetate, nickel chloride.
The third aspect, the present invention provide a kind of sodium-ion battery cathode, contain any of the above-described kind of multistage composite metal oxygen
Compound material.
Fourth aspect, the present invention provide a kind of sodium-ion battery, contain above-mentioned sodium-ion battery cathode.
Sodium-ion battery high rate performance of the invention is excellent, and preferable charge/discharge capacity is still able to maintain under high current.
Detailed description of the invention
Fig. 1 is scanning electron microscope (SEM) photo of the multistage composite metal oxide materials of an embodiment of the present invention.
Fig. 2 is X-ray diffraction (XRD) map of the multistage composite metal oxide materials of an embodiment of the present invention.
Fig. 3 is the constant current charge-discharge test result of the multistage composite metal oxide materials of an embodiment of the present invention.
Specific embodiment
The present invention is further illustrated below in conjunction with attached drawing and following embodiments, it should be appreciated that attached drawing and following embodiments
It is merely to illustrate the present invention, is not intended to limit the present invention.
It is disclosed a kind of multistage composite metal oxide materials.Fig. 1 shows the multistage composite of an embodiment of the present invention
The SEM photograph of metal oxide materials.As shown in Figure 1, the multistage composite metal oxide materials include tubulose carbon skeleton and
It is grown on the metal composite oxide on tubulose carbon skeleton surface.
The length of tubulose carbon skeleton can be 0.1~0.8 μm, and caliber can be 50~100nm, and pipe thickness can be 5~50nm.
Metal composite oxide may include ferriferous oxide and cupro-nickel compound (corronil).Ferriferous oxide and cupro-nickel are compound
Ferriferous oxide can effectively provide charge-discharge performance in the combination of object, and corronil structured catalysis ferriferous oxide realizes quickly electrification
Reaction process is learned, corronil can show more excellent catalytic reaction activity compared with other transition metal oxides.
Wherein, ferriferous oxide Fe23.33O32.The ferriferous oxide is non-stoichiometric composition, and electric conductivity is higher than three oxidations
Two iron, charge-discharge power process can be effectively facilitated.
Cupro-nickel compound can be Cu0.81Ni0.19.The cupro-nickel compound can be catalyzed ferriferous oxide and realize quick electrochemistry
Reaction process, corronil can show more excellent catalytic reaction activity compared with other transition metal oxides.
The molar ratio of ferriferous oxide and cupro-nickel compound can be 5:1~1:5.Under the proportional region, cupro-nickel may be implemented
Effective synergy of the performance of the catalytic effect and ferriferous oxide of alloy, had not only met the performance of ferriferous oxide but also had been able to achieve cupro-nickel
Catalytic effect.
Metal composite oxide can be in granular form, and partial size is, for example, 30~500nm.With other patterns such as sheet phase
Effective electrical contact between can promoting than, this nutty structure, for the pattern accumulated each other, nutty structure energy
The most effective transmitting for realizing charge.
The ratio of tubulose carbon skeleton and metal composite oxide is adjustable, such as its mass ratio can be 1:5~1:20.This ratio
Under example, enough carbon backbone structure support active materials are provided while can effectively realizing the performance of active material.
The disclosure multistage composite metal oxide materials (or " carbon make skeletal support growth metal oxide it is compound
Metal oxide ") Solid phase synthesis can be passed through.Hereinafter, as an example, illustrating preparation method.
Firstly, preparing carbon skeleton.In some embodiments, organic carbon source pyrolysis is prepared into carbon skeleton, obtains product A.Have
Machine carbon source can be selected from urea, ethylenediamine tetra-acetic acid (EDTA), citric acid, melamine, poly-methyl pyrrole alkanone etc..These are organic
Carbon source can be pyrolyzed polymerization under the high temperature conditions, and generate layer structure, and layer structure can crimp under transition metal effect
Form tubular structure.These organic matters are easy to produce tubular structure because of itself polycondensation reaction.Pyrolysis temperature can be according to organic
Carbon source selects, such as can be 300~600 DEG C.Pyrolysis time may be, for example, 1min~3h.
Product A is uniformly mixed with copper source and source of iron.Product A and the mass ratio of copper source and source of iron can be (1~2): (3~
4): (5~10), for example, 2:2:5~2:2:9.Under the ratio, the collaboration that can satisfy carbon, copper, ferriferous oxide promotes electrification
Learn the effect of reaction.By adjusting the ratio, the ratio of carbon skeleton, copper, ferro element in adjustable products therefrom, in turn
Adjust the chemical property of product.Copper source can be mantoquita, such as copper acetate, cupric oxalate, copper citrate or its hydrate etc..Wherein
It is preferred that copper acetate and/or its hydrate, restore to obtain metal simple-substance because it easily discharges reducibility gas at high temperature.Source of iron can
For molysite, such as ferric nitrate, ammonium ferric oxalate, ironic citrate or its hydrate etc..Wherein preferred ferric nitrate, because of the raw material
Easily composite construction is formed in carbon material surface nucleating growth.
In some embodiments, first by product A and copper source and source of iron mixed grinding, be then completely dissolved in water obtain it is molten
Acquired solution is freeze-dried by liquid, obtains fully dispersed and without the powder obviously reunited, which is conducive to each component and sufficiently reacts
To obtain the final composite construction of the present invention.The powder is the homogeneous mixture of product A and copper source and source of iron.Freeze-drying can be with
It is carried out in freeze drier, freeze-drying temperature can be -50 DEG C~-5 DEG C (such as -50 DEG C), and the time can be 24~72h.
Product A and the homogeneous mixture of copper source and source of iron are pyrolyzed, the carbon skeleton with metal oxide is made, obtains
To product B.Pyrolysis temperature can be 500~700 DEG C.If temperature is too low, native copper cannot be gone back and obtain metal simple-substance；If warm
Height is spent, then carbon structure may be made to destroy.In some embodiments, it can be warming up to the heating rate of 5~10 DEG C/min
Pyrolysis temperature.The reaction rate that can satisfy carbon source and copper source using the heating rate is close, can grow to obtain composite junction simultaneously
Structure.
Product B is uniformly mixed with nickel source.Product B and the mass ratio of nickel source can be 10:1~6:1.It, can under the ratio
It is generated with obtaining corronil without extra nickel oxide.By adjusting the ratio, nickel element in adjustable products therefrom
Content, and then adjust product chemical property.Nickel source can be nickel salt, such as nickel nitrate, nickel acetate, nickel chloride or its hydration
Object etc..Wherein preferred nickel nitrate and/or its hydrate, because decomposition product easily disperses to obtain the lesser granule-morphology of size.
In some embodiments, first by product B and nickel source mixed grinding, then it is completely dissolved in water and obtains solution, it will
Obtained material is the homogeneous mixture of product B and nickel source after acquired solution is dry, avoids nickel source from being unevenly distributed so that the later period is anti-
It cannot should effectively obtain corronil compound.Drying means can be freeze-drying.It is obtained after drying in a manner of freeze-drying
It is chip solid.Freeze-drying can carry out in freeze drier, and freeze-drying temperature can be -50 DEG C~-5 DEG C (such as -50
DEG C), the time can for 12~for 24 hours.
The homogeneous mixture of product B and nickel source are pyrolyzed, obtain product C, predominantly copper, iron, nickel metal simple-substance with
The composite construction of carbon.Pyrolysis temperature can be 500~700 DEG C.If temperature is too low, reduction reaction cannot be completed；If warm
Height is spent, then carbon structure is destroyed.In some embodiments, pyrolysis temperature can be warming up to the heating rate of 5~10 DEG C/min
Degree.Decomposition product can be made easily to disperse to obtain the lesser granule-morphology of size using the heating rate.
Using above-mentioned pyrolysis sequence, can successively be pyrolyzed to realize that the preparation of corronil structure, directly pyrolysis are then held
It is also easy to produce nickel metal simple-substance, above-mentioned composite construction cannot be obtained.
Product C is pyrolyzed, achievees the purpose that activating iron obtains ferriferous oxide, carbon is obtained and makees skeletal support growth metal
The metal composite oxide of oxide.Pyrolysis temperature can be 200 ~ 300 DEG C.If temperature is too low, cannot activate；If warm
Height is spent, then carbon-coating is destroyed.Pyrolysis time can be 0.1 ~ 5 hour.
Iron is preferentially oxidized to form ferriferous oxide under the above process, corronil can be kept under the above process not by
Oxidation.
The method that present embodiment uses can obtain carbon skeleton, corronil and ferriferous oxide simultaneously, with other technologies
It compares, it is easier to obtain the compound pattern of a variety of different conditions structures (carbon-alloy-nonstoichiometric metal oxide).
Compared with prior art, it is environmental-friendly, next to have the advantages that raw material used by the disclosure has for the disclosure
The advantages that source is extensive, low in cost, used preparation method are easily operated.The disclosure has carbon skeleton using Solid phase synthesis
Multi-element metal oxide negative electrode material, tubular precursor is prepared by simple technique, then obtain by aoxidizing predecessor
The good battery cathode of comprehensive performance.Stability when nickel is conducive to improve cycle performance and high rate charge-discharge is added.For
In the pyrolytic process of final step, metallic iron simple substance is oxidized, then can improve material capacity, metal oxide charge/discharge capacity compared with
It is high.The addition of copper improves battery capacity.It is compound to carry out multiphase, better chemical property can be obtained in conjunction with each material characteristics.
The capacity that metal composite oxide has both metal oxide as anode material of lithium-ion battery, due to it is big and raw material is cheap
The characteristics of, it has broad prospects, and it is joined together with fixed skeleton structure, then it is steady further to play structure
It is fixed, so that stable circulation.Therefore the mode that this kind grows metal oxide on carbon pipe has extremely important effect, can be more
Mend defect of the metal oxide as negative electrode material.
Enumerate embodiment further below with the present invention will be described in detail.It will similarly be understood that following embodiment is served only for this
Invention is further described, and should not be understood as limiting the scope of the invention, those skilled in the art is according to this hair
Some nonessential modifications and adaptations that bright above content is made all belong to the scope of protection of the present invention.Following examples are specific
Technological parameter etc. is also only an example in OK range, i.e. those skilled in the art can be done properly by the explanation of this paper
In the range of select, and do not really want to be defined in hereafter exemplary specific value.
Embodiment 1
The urea of certain mass is taken, grinding uniformly, is pyrolyzed 0.5 hour at 350 DEG C in Muffle furnace and prepares carbon skeleton, obtain product
A1。
2:2:1 in mass ratio weighs copper acetate dihydrate, Fe(NO3)39H2O, product A1 and is placed in glass mortar, sufficiently
Grinding, obtains blue-green mixture, 50 mL deionized waters is added into above-mentioned raw materials, and 12h is stirred on magnetic stirring apparatus makes it
Sufficiently dissolution, obtains blue-green clear transparent solutions, which is freeze-dried, obtain blue-green powder, be placed in Muffle furnace
Pyrolysis, pyrolysis actual temp are 500 DEG C, and heating rate is 5 DEG C/min, keeps the temperature 1 h, and the carbon bone with metal oxide is made
Frame obtains product B1.
Product B1 and nickel nitrate are weighed according to mass ratio 10:1, ground and mixed is uniform in glass mortar, and 50 mL are added and go
Ionized water, stirring dissolves it sufficiently on magnetic stirring apparatus, obtains celadon mixture, and the mixture is dry using freezing
Dry, freeze-drying temperature is -50 DEG C, and time 12h obtains celadon chip solid.The solid is packed into crucible, is placed in tubular type
It is pyrolyzed in furnace, heating rate is 5 DEG C/min, rises to 500 DEG C, keeps the temperature 1 h.Obtain product C1.
Product C1 is put into Muffle furnace and is pyrolyzed 0.5 hour for 300 DEG C, achievees the purpose that activation, obtains carbon and make skeletal support
Grow the metal composite oxide of metal oxide.
The JSM-6700F type scanning electron microscope that resulting product is produced with Japan Electronics Corporation is observed, it can
Significantly to see tubular armature, surface growth is metal composite oxide there are many grain structure, sees Fig. 1.Tubular armature
Length is 300nm, caliber 50nm, and with a thickness of 5nm, the partial size of metal composite oxide particle is 30nm.By resulting product
Particle analyzes sample with Rigaku D/max2000PCX- x ray diffractometer x, and product is ferriferous oxide, copper, nickel composite parts.
Embodiment 2
The EDTA of certain mass is taken, grinding uniformly, is pyrolyzed 0.1 hour (6 minutes) at 400 DEG C in Muffle furnace and prepares carbon skeleton,
Obtain product A2.
1:1:1 in mass ratio weighs copper acetate dihydrate, Fe(NO3)39H2O, product A2 and is placed in glass mortar, sufficiently
Grinding, obtains blue-green mixture, 50 mL deionized waters is added into above-mentioned raw materials, and 12h is stirred on magnetic stirring apparatus makes it
Sufficiently dissolution, obtains blue-green clear transparent solutions, which is freeze-dried, obtain blue-green powder, be placed in Muffle furnace
Pyrolysis, pyrolysis actual temp are 600 DEG C, and heating rate is 6 DEG C/min, keep the temperature 1 h.The carbon bone with metal oxide is made
Frame obtains product B2.
Product B2 and nickel nitrate are weighed according to mass ratio 9:1, ground and mixed is uniform in glass mortar, and 50 mL are added and go
Ionized water, stirring dissolves it sufficiently on magnetic stirring apparatus, obtains celadon mixture, which is freeze-dried, cold
Freezing drying temperature is -50 DEG C, and time 16h obtains celadon chip solid.The solid is packed into crucible, is placed in tube furnace
Pyrolysis, heating rate are 10 DEG C/min, rise to 600 DEG C, keep the temperature 1 h.Obtain product C2.
Product C2 is put into 300 DEG C of pyrolysis 1h in Muffle furnace, achievees the purpose that activation, carbon is obtained and makees skeletal support growth gold
Belong to the metal composite oxide of oxide.
The XRD diagram of products therefrom is shown in that Fig. 2, product are ferriferous oxide, copper, nickel composite parts.
Embodiment 3
The citric acid of certain mass is taken, grinding uniformly, is pyrolyzed 1 hour at 300 DEG C in Muffle furnace and prepares carbon skeleton, obtain product
A3。
2:2:3 in mass ratio weighs copper acetate dihydrate, Fe(NO3)39H2O, product A3 and is placed in glass mortar, sufficiently
Grinding, obtains blue-green mixture, 50 mL deionized waters is added into above-mentioned raw materials, and 12h is stirred on magnetic stirring apparatus makes it
Sufficiently dissolution, obtains blue-green clear transparent solutions, which is freeze-dried, obtain blue-green powder, be placed in Muffle furnace
Pyrolysis, pyrolysis actual temp are 700 DEG C, and heating rate is 7 DEG C/min, keep the temperature 1 h.The carbon bone with metal oxide is made
Frame obtains product B3.
Product B3 and nickel nitrate are weighed according to mass ratio 7:1, ground and mixed is uniform in glass mortar, and 50 mL are added and go
Ionized water, stirring dissolves it sufficiently on magnetic stirring apparatus, obtains celadon mixture, which is freeze-dried, cold
Freezing drying temperature is -50 DEG C, and time 18h obtains celadon chip solid.The solid is packed into crucible, is placed in tube furnace
Pyrolysis, heating rate are 10 DEG C/min, rise to 700 DEG C, keep the temperature 1 h.Obtain product C3.
Product C3 is put into 300 DEG C of pyrolysis 0.7h in Muffle furnace, achievees the purpose that activation, obtains carbon and make skeletal support growth
The metal composite oxide of metal oxide.
XRD shows that product is ferriferous oxide, copper, nickel composite parts.
Embodiment 4
The urea of certain mass is taken, uniformly, 450 DEG C of pyrolysis prepare carbon skeleton in 0.6 hour in Muffle furnace for grinding, obtain product
A4。
1:1:2 in mass ratio weighs copper acetate dihydrate, Fe(NO3)39H2O, product A4 and is placed in glass mortar, sufficiently
Grinding, obtains blue-green mixture, 50 mL deionized waters is added into above-mentioned raw materials, and 12h is stirred on magnetic stirring apparatus makes it
Sufficiently dissolution, obtains blue-green clear transparent solutions, which is freeze-dried, obtain blue-green powder, be placed in Muffle furnace
Pyrolysis, pyrolysis actual temp are 700 DEG C, and heating rate is 7 DEG C/min, keep the temperature 1 h.The carbon bone with metal oxide is made
Frame obtains product B4.
Product B4 and nickel nitrate are weighed according to mass ratio 6:1, ground and mixed is uniform in glass mortar, and 50 mL are added and go
Ionized water, stirring dissolves it sufficiently on magnetic stirring apparatus, obtains celadon mixture, which is freeze-dried, cold
Freezing drying temperature is -50 DEG C, and the time is for 24 hours, to obtain celadon chip solid.The solid is packed into crucible, is placed in tube furnace
Pyrolysis, heating rate are 15 DEG C/min, rise to 700 DEG C, keep the temperature 1 h.Obtain product C4.
Product C4 is put into 300 DEG C of pyrolysis 1.2h in Muffle furnace, achievees the purpose that activation, obtains carbon and make skeletal support growth
The metal composite oxide of metal oxide.
XRD shows that product is ferriferous oxide, copper, nickel composite parts.
Electrochemical property test
The resulting product of each embodiment is prepared into button sodium-ion battery, specific encapsulation step is as follows: activity powder is (each
The resulting product of embodiment), conductive agent (super-p), bonding agent (carboxyl methyl cellulose) matching according to mass ratio 8:1:1
After more uniform than grinding, slurry is made, uniformly slurry is applied on copper foil with coating device, then in 80 DEG C of dryings of vacuum oven
12h.Electrode slice is assembled into sodium ion half-cell later, constant current charge-discharge survey is carried out to battery using new prestige electrochemical workstation
Examination, test voltage 0.01-3.0V, test current density size are 0.1 and 0.5A g-1.The test result of embodiment 3 is shown in figure
3, it is known that the high rate performance of material is excellent, and preferable charge/discharge capacity is still able to maintain under high current.
Claims (8)
1. a kind of multistage composite metal oxide materials characterized by comprising tubulose carbon skeleton and be grown on the pipe
The metal composite oxide on shape carbon skeleton surface, the metal composite oxide include the composite junction of ferriferous oxide and corronil
Structure.
2. multistage composite metal oxide materials according to claim 1, which is characterized in that the length of the tubulose carbon skeleton
Degree is 0.1~0.8 μm, and caliber is 50~100nm, and pipe thickness is 5~50nm.
3. multistage composite metal oxide materials according to claim 1 or 2, which is characterized in that the ferriferous oxide is
Fe23.33O32, the copper-nickel alloy is Cu0.81Ni0.19。
4. multistage composite metal oxide materials according to any one of claim 1 to 3, which is characterized in that iron oxidation
The molar ratio of object and corronil is 5:1~1:5.
5. multistage composite metal oxide materials according to any one of claim 1 to 4, which is characterized in that described multiple
It closes metal oxide to be in granular form, it is preferable that partial size is 30~500nm.
6. multistage composite metal oxide materials according to any one of claim 1 to 5, which is characterized in that tubulose carbon
The mass ratio of skeleton and metal composite oxide is 1:5~1:20.
7. a kind of sodium-ion battery cathode, which is characterized in that contain multistage composite gold described in any one of claims 1 to 6
Belong to oxide material.
8. a kind of sodium-ion battery, which is characterized in that contain sodium-ion battery cathode as claimed in claim 7.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1569623A (en) * | 2004-04-22 | 2005-01-26 | 华中师范大学 | Preparation for composite material with nanometal or metal oxide distributed on surface of carbon nanotube uniformly |
| CN104269534A (en) * | 2014-07-31 | 2015-01-07 | 浙江大学 | Preparation method of graphene oxide and graphene oxide composite material and use of graphene oxide and graphene oxide composite material in sodium-ion battery |
| CN107253713A (en) * | 2017-07-05 | 2017-10-17 | 中国石油大学(北京) | A kind of length, caliber and the controllable CNT of wall thickness and preparation method thereof |
| CN107634198A (en) * | 2017-09-03 | 2018-01-26 | 河南师范大学 | Alkaline secondary cell negative electrode material [NixCuyFe2O4] and using the negative material battery |
| CN108539185A (en) * | 2018-05-24 | 2018-09-14 | 中南大学 | A kind of lithium or anode material of lithium-ion battery and preparation method thereof |
-
2019
- 2019-03-13 CN CN201910189491.1A patent/CN109950486B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1569623A (en) * | 2004-04-22 | 2005-01-26 | 华中师范大学 | Preparation for composite material with nanometal or metal oxide distributed on surface of carbon nanotube uniformly |
| CN104269534A (en) * | 2014-07-31 | 2015-01-07 | 浙江大学 | Preparation method of graphene oxide and graphene oxide composite material and use of graphene oxide and graphene oxide composite material in sodium-ion battery |
| CN107253713A (en) * | 2017-07-05 | 2017-10-17 | 中国石油大学(北京) | A kind of length, caliber and the controllable CNT of wall thickness and preparation method thereof |
| CN107634198A (en) * | 2017-09-03 | 2018-01-26 | 河南师范大学 | Alkaline secondary cell negative electrode material [NixCuyFe2O4] and using the negative material battery |
| CN108539185A (en) * | 2018-05-24 | 2018-09-14 | 中南大学 | A kind of lithium or anode material of lithium-ion battery and preparation method thereof |
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