CN104577076A - Tin-based ternary alloy negative active material and preparation method thereof - Google Patents
Tin-based ternary alloy negative active material and preparation method thereof Download PDFInfo
- Publication number
- CN104577076A CN104577076A CN201310470513.4A CN201310470513A CN104577076A CN 104577076 A CN104577076 A CN 104577076A CN 201310470513 A CN201310470513 A CN 201310470513A CN 104577076 A CN104577076 A CN 104577076A
- Authority
- CN
- China
- Prior art keywords
- solution
- ternary
- tin
- alloy material
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C13/00—Alloys based on tin
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
-
- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/387—Tin or alloys based on tin
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides a tin-based ternary alloy negative active material and a preparation method thereof, and concretely provides a ternary alloy negative material A1-xBxSn5 and a preparation method thereof. In the above formula, x is not lower than 0.01 and not greater than 0.99. The negative active material provided by the invention has higher theoretic specific capacity and better cycle stability than other tin-based alloy materials.
Description
Technical field
The invention belongs to technical field of lithium ion battery negative, be specifically related to a kind of tinbase ternary alloy active cathode material and preparation method thereof.
Background technology
Along with the develop rapidly of mobile electronic device, the performance of people to chemical power source is had higher requirement.Lithium ion battery has because of it advantage that specific energy is large, monomer voltage is high, self-discharge is little, is widely used in the electronic products such as mobile phone, notebook computer, digital camera, will be applied to the fields such as the storage of electromobile and renewable energy source further.It is wherein the important component part of lithium ion battery as the negative material improving energy capacity of battery and cycle life.Tin base alloy anode material has that theoretical capacity is high, processibility good, electroconductibility is high, can fast charging and discharging, compare the many merits such as the susceptibility of environment is low with carbon negative pole material, receive increasing concern.
But Sn alloy material of cathode also also exists huge volumetric expansion problem, the cycle performance of material is caused to be deteriorated.The method improving Sn material electrochemical performance has a lot, comprise that nanometer, carbon are coated, alloying, non-crystalline state process etc.
At present, an a lot of section is had about the document patent improving tin base alloy anode material chemical property both at home and abroad.Be the most successfully wherein Sn, Co, C negative material prepared by Sony corporation of Japan, this material successfully achieves commercialization.Wherein Co, adding of C element material is made to maintain excellent cycle performance.But Theil indices is less in material, thus capacity is lower.
Publication number disclosed in December, 2012 is tin-amorphous NiTi composite film cathode material that the Chinese invention patent application of CN102832377A discloses a kind of magnetron sputtering method and prepares, and this material has good cycle performance.But magnetron sputtering deposition method sedimentation rate is low, equipment is complicated, cost is higher.Meanwhile, also there is the low problem of theoretical capacity in material.
In sum, this area still lacks that a kind of theoretical capacity is high, and cost is low, the negative material of good cycling stability.
Summary of the invention
The object of the present invention is to provide a kind of theoretical capacity high, cost is low, the negative material of good cycling stability.
A first aspect of the present invention, provides a kind of ternary-alloy material, and described material has the composition be shown below:
A
1-xb
xsn
5formula I
Wherein, A, B are for being selected from lower group: any two kinds in Fe, Ni, Co, Cu, and 0.01≤x≤0.99;
And described ternary-alloy material has Tetragonal.
In another preference, described ternary-alloy material belongs to P4/mcc spacer.
In another preference, described A is Fe, B is Co.
In another preference, in described material, the content of Sn is 60-99wt%, by the total weight of ternary-alloy material.
In another preference, in described material, the content of Sn is 70-97wt%, is preferably 80-95wt%.
In another preference, described material morphology can be any form, comprises powder, block, particle etc.
In another preference, its pattern is spherical or is similar to spherical (being generally " spherical particle ").
In another preference, described material is nano particle, and general particle diameter is 10-100nm, is preferably 20-70nm, is more preferably 30-50nm.
In another preference, described spherical particle material surface also has zone of oxidation.
In another preference, the thickness of described zone of oxidation is 1-10nm, is preferably 2-6nm, is more preferably 3-4nm.
In another preference, described material has good monodispersity.
A second aspect of the present invention, provide a kind of preparation method of material as described in the first aspect of the invention, the method preparation of described material by being selected from lower group: coprecipitation method, hydrothermal synthesis method, molte-salt synthesis, sol-gel method, sonochemical method, wet chemical method, mechanochemistry method, vacuum arc furnace melting method, planetary type ball-milling method, electrodip process, magnetron sputtering method, plasma reaction method.
In another preference, described method comprises step:
I () provides Sn ion source solution;
(ii) in the presence of a reducing agent, make the Sn ion reduction in Sn ion source solution, obtain the first solution mixture containing simple substance tin;
(iii) source of iron reagent, cobalt source reagent are mixed with above-mentioned first solution mixture, obtain the second solution mixture;
(iv) under the reducing conditions, make the reducing metal ions in described second solution mixture be simple substance, form the ternary-alloy material shown in formula II;
Fe
1-xco
xsn
5formula II
Wherein, A, B are for being selected from lower group: any two kinds in Fe, Ni, Co, Cu, and in formula, 0.01≤x≤0.99.
In another preference, described Sn ion source solution is the solution containing Sn ion.
In another preference, described step (i)-(iii) carries out at 100-170 DEG C.
In another preference, described step (iv) is carried out at 150 DEG C-190 DEG C.
In another preference, in described step (ii)-(iv), also comprise: the solution mixture described in strong stirring.
In another preference, described Sn ion source solution is prepared by the following method:
In inert environments, Sn presoma is injected in organic solvent, obtains Sn ion source solution;
Preferably, described organic solvent is the organic solvent containing surface stabilizer.
In another preference, described method comprises the one or more features being selected from lower group:
Described Sn presoma is tin salt solution; And/or
Described surface stabilizer is selected from lower group: polyvinylpyrrolidone (PVP), cetyl trimethylammonium bromide (CTAB), oleyl amine, poly-(2-ethyl-2 oxazoline) (PEtOx), or its combination; And/or
Described organic solvent is selected from lower group: Virahol, ethylene glycol, diethanolamine, Tetraglycol 99, or its combination; And/or
Described reductive agent is selected from lower group: sodium borohydride, hydrazine hydrate, inferior sodium phosphate, active metal, or its combination; And/or
Described source of iron reagent is molysite or the solution containing ferric ion; And/or
Described cobalt source reagent is cobalt salt or the solution containing cobalt ion.
In another preference, described tin salt solution is selected from lower group: the sub-tin of stannous sulfate, tin protochloride, nitric acid, or its combination.
In another preference, described active metal is the metal that reductibility is stronger than Sn, and preferably, described active metal is selected from lower group: potassium, calcium, sodium, magnesium, aluminium, zinc, iron, or its combination.
In another preference, described source of iron reagent is selected from lower group: Fe
2(SO
4)
3, Fe (NO
3)
3, FeCl
3, or its combination; Or Fe
2(SO
4)
3solution, Fe (NO
3)
3solution, FeCl
3solution, or its combination.
In another preference, described cobalt source reagent is selected from lower group: CoCl
2, CoBr
2, Co (NO
3)
2, CoSO
4, or its combination; Or CoCl
2solution, CoBr
2solution, Co (NO
3)
2solution, CoSO
4solution, or its combination.
In another preference, described solution is organic solution or the aqueous solution.
In another preference, in step (ii), described reductive agent is added by dropping mode.
A third aspect of the present invention, provides the purposes of ternary-alloy material as described in the first aspect of the invention for the preparation of battery cathode active material.
A fourth aspect of the present invention, provide a kind of battery cathode active material, described material contains ternary-alloy material as described in the first aspect of the invention.
A fifth aspect of the present invention, provides a kind of battery, and described battery contains the ternary-alloy material described in first aspect present invention or the battery cathode active material described in fourth aspect present invention.
A sixth aspect of the present invention, provides a kind of goods, and described goods contain the ternary-alloy material described in first aspect present invention or are made up of the ternary-alloy material described in first aspect present invention.
In another preference, described goods comprise battery (preferred lithium ionization cell), cell negative electrode material.
Should be understood that within the scope of the present invention, above-mentioned each technical characteristic of the present invention and can combining mutually between specifically described each technical characteristic in below (eg embodiment), thus form new or preferred technical scheme.As space is limited, tiredly no longer one by one to state at this.
Accompanying drawing explanation
Fig. 1 is Fe prepared in the embodiment of the present invention 4
0.5co
0.5sn
5the XRD figure of ternary alloy anode material.
Fig. 2 is Fe prepared in the embodiment of the present invention 1
0.2co
0.8sn
5the SEM figure of ternary alloy anode material.
Fig. 3 is Fe prepared in the embodiment of the present invention 4
0.5co
0.5sn
5the energy spectrogram of ternary alloy anode material.
Fig. 4 is Fe prepared in the embodiment of the present invention 1
0.2co
0.8sn
5the HRTEM figure of ternary alloy anode material.
Embodiment
The present inventor, through long-term and deep research, has unexpectedly prepared a kind of ternary-alloy material A of Sn base
1-xb
xsn
5, wherein 0.01≤x≤0.99, described material is ternary alloy cenotype (Tetragonal).And when described A is iron and B is Co, above-mentioned materials has very high theoretical capacity and good cycle performance, is suitable for very much preparing negative active core-shell material.Based on above-mentioned discovery, contriver completes the present invention.
There is the ternary-alloy material of tetragonal phase
Pure ternary alloy phase, as AuCuSn
2deng, generally all more difficult synthesis, is used in catalytic field mostly, lies down very much the application of negative material.Mostly ternary alloy of the prior art, be to be compounded with carbon material, as document Synthesis and Properties of Sn
30co
30c
40the ternary alloy mentioned in Ternary Alloy Anode Material forLithium Ion Battery, or three kinds of metals deposit or compound, as the ternary alloy etc. mentioned in document Electrodeposition and electrochemical investigation of thin film Sn-Co-Ni alloyanode for lithium-ion batteries.Above-mentioned ternary alloy does not all form a phase jointly.And in material provided by the invention, three kinds of metals together constitute Tetragonal, and extremely unexpectedly there is very high theoretical capacity and cyclical stability, can battery cathode active material be used as.
Material provided by the invention, has as shown in the formula the composition shown in I:
A
1-xB
xSn
5
Wherein, A, B are selected from lower group independently of one another: Fe, Ni, Co, Cu.
0.01≤x≤0.99；
And described ternary-alloy material has Tetragonal.
In another preference, described ternary-alloy material belongs to P4/mcc spacer.
In another preference, described A is Fe, B is Co.
Tinbase ternary alloy anode material
As used herein, term " tin-based alloy " refers to the alloy material formed as main component and one or more metals using tin.Especially, in the present invention, " tinbase ternary alloy " refers to using tin as main component, in the alloy material that other two kinds of metals are formed jointly.Preferred tinbase ternary alloy of the present invention is Fe
1-xco
xsn
5ternary alloy.
In theory, a tin atom can form alloy with 4.4 lithium atoms, and this makes tin have quite high reversible electrode capacity, is used for lithium ion battery illustrates wide Research Prospects to tin-based material; But tin metal itself makes negative pole but great deficiency, its disadvantage is exactly that cycle life is too short.In order to utilize the advantage of tin metal, solve the deficiency that its exists, this area adopts other element that to adulterate in tin metal to form the means of tin-based alloy or mixture usually simultaneously.
In order to contribute to that the present invention is described, the present inventor provides following invention mechanism for reference.Should be understood that the present invention not by the restriction of this mechanism, and this mechanism also may need to revise.
In ternary alloy anode material of the present invention, for Fe-Co-Sn ternary alloy, Sn element can provide higher theoretical capacity, and Fe element can improve the coulombic efficiency that negative material circulates first effectively, adding of Co element, significantly improves the cyclical stability of material.Therefore, the battery of ternary-alloy material of the present invention is adopted to have the advantages such as theoretical specific capacity is high, circulating battery good stability.
Especially, a kind of ternary alloy of constituent optimization has the composition be shown below:
Fe
1-xCo
xSn
5
In described material, Sn is principal constituent, content usually >=50wt%, as in a preference of the present invention, the content range of Sn is 60-99wt%.
In another preference, in described material, the content of Sn is 70-97wt%, is preferably 80-95wt%.
The scope of described x has no particular limits, and as 0.01-0.99, being preferably 0.1-0.9, is more preferably 0.2-0.8.
Described material can be any form, is preferably spherical particle form.In another preference, described spherical particle material surface also has zone of oxidation.
The particle diameter of described spherical particle material has no particular limits, and is generally≤200nm.In another preference, the particle diameter of described spherical particle material is 10-100nm, is preferably 20-70nm, is more preferably 30-50nm.
The thickness of described zone of oxidation is not particularly limited, and in another preference, the thickness of described zone of oxidation is 1-10nm, is preferably 2-6nm, is more preferably 3-4nm.
Described material can be prepared by any prior art, as passed through coprecipitation method, hydrothermal synthesis method, molte-salt synthesis, sol-gel method, sonochemical method, wet chemical method, mechanico-chemical reaction (such as mechanical alloying method and mechanical attrition method), vacuum arc furnace melting, planetary type ball-milling method, electrodip process, magnetron sputtering method, plasma reaction method etc.
The preparation of tinbase ternary alloy anode material
Present invention also offers a kind of preparation method of tinbase ternary alloy anode material, particularly, method of the present invention comprises the steps:
Present invention also offers a kind of preparation method of tinbase ternary alloy anode material, particularly, method of the present invention comprises the steps:
For wet-chemical reaction method, specifically comprise the following steps:
I () provides a Sn ion source solution;
(ii) in the presence of a reducing agent, make the Sn ion reduction in Sn ion source solution, obtain the first solution mixture containing simple substance tin;
(iii) A source reagent, B element source reagent are mixed with above-mentioned first solution mixture, obtain the second solution mixture;
(iv) under the reducing conditions, make the reducing metal ions in described second solution mixture be simple substance, form the ternary-alloy material shown in formula I;
A
1-xb
xsn
5formula I
In formula, 0.01≤x≤0.99.
In another preference, described Sn ion source solution is the solution containing Sn ion.
With Fe
1-xco
xsn
5preparation method be example, specifically comprise the following steps:
I () provides a Sn ion source solution;
(ii) in the presence of a reducing agent, make the Sn ion reduction in Sn ion source solution, obtain the first solution mixture containing simple substance tin;
(iii) source of iron reagent, cobalt source reagent are mixed with above-mentioned first solution mixture, obtain the second solution mixture;
(iv) under the reducing conditions, make the reducing metal ions in described second solution mixture be simple substance, form the ternary-alloy material shown in formula II;
Fe
1-xco
xsn
5formula II
In formula, 0.01≤x≤0.99.
In another preference, described Sn ion source solution is the solution containing Sn ion.
Described Sn ion source solution can be bought by commercially available approach, also can be obtained by any conventional method of this area.As in a preference of the present invention, described solution can be prepared by the following method:
In inert environments, Sn presoma is injected in organic solvent, obtains Sn ion source solution;
Preferably, described organic solvent is the organic solvent containing surface stabilizer.
Described Sn presoma can be can provide Sn ion arbitrarily, or reacts with organic solvent the material producing Sn ion.Preferably, Sn presoma of the present invention is tin salt solution.
In another preference, described tin salt solution is selected from lower group: the sub-tin of stannous sulfate, tin protochloride, nitric acid, or its combination.
Described surface stabilizer can be the material that can increase arbitrarily stability of solution, as comprised the surface stabilizer of group under (but being not limited to): polyvinylpyrrolidone (PVP), cetyl trimethylammonium bromide (CTAB), oleyl amine, poly-(2-ethyl-2 oxazoline) (PEtOx), or its combination.
The kind of described organic solvent is not particularly limited, and is preferably organic proton solvent, as comprised (but being not limited to) following solvent: Virahol, ethylene glycol, diethanolamine, Tetraglycol 99, or its combination.
In step (ii), described reductive agent is not particularly limited, and can be the reductive agent that Sn ion (divalence or tetravalence) can be reduced to arbitrarily Sn simple substance.Reductive agent preferably for being selected from lower group: sodium borohydride, hydrazine hydrate, inferior sodium phosphate, active metal, or its combination.
In another preference, described active metal is the metal that reductibility is stronger than Sn, and preferably, described active metal is selected from lower group: potassium, calcium, sodium, magnesium, aluminium, zinc, iron, or its combination.
Described source of iron reagent can be the material arbitrarily containing ferro element, as fe, molysite or the solution containing iron ion, is preferably trivalent iron salt, or the solution containing ferric ion.
Described cobalt source reagent can be the material arbitrarily containing cobalt element, as simple substance cobalt, cobalt salt or the solution containing cobalt ion, is preferably divalent cobalt, or the solution containing divalent cobalt ion.
In another preference, described source of iron reagent is selected from lower group: Fe
2(SO
4)
3, Fe (NO
3)
3, FeCl
3, or its combination; Or Fe
2(SO
4)
3solution, Fe (NO
3)
3solution, FeCl
3solution, or its combination.
In another preference, described cobalt source reagent is selected from lower group: CoCl
2, CoBr
2, Co (NO
3)
2, CoSO
4, or its combination; Or CoCl
2solution, CoBr
2solution, Co (NO
3)
2solution, CoSO
4solution, or its combination.
In another preference, described solution is organic solution or the aqueous solution.
In another preference, in step (ii), described reductive agent is added by dropping mode, to control speed of reaction, guarantees the form of product metal simple substance.
In the present invention, a kind of preferred preparation method is as follows:
1) under argon gas, heating condition, tin presoma is injected in the organic solvent containing surface stabilizer, strong stirring, obtains uniform tin-salt solution.
2) slowly dropping goes back original reagent, the rapid blackening of tin-salt solution, strong stirring, obtains simple substance tin nanoparticles.
3) add the iron, the cobalt solvent that configure by different molar percentage, heat up simultaneously, strong stirring a few hours.Reaction terminates, slowly cool to room temperature.
4) washing, centrifugal gained nano-metal particle, drying at room temperature.
In step 1) in, described tin presoma refers to tin salt solution;
Preferably, described presoma is one or more in stannous sulfate, tin protochloride, the sub-tin of nitric acid.
Preferably, in step 1) in, described surface stabilizer is one or more in polyvinylpyrrolidone (PVP), cetyl trimethylammonium bromide (CTAB), oleyl amine, poly-(2-ethyl-2 oxazoline) (PEtOx).
Preferably, in step 1) in, described organic solvent is one or more in Virahol, ethylene glycol, diethanolamine, Tetraglycol 99.
Preferably, in step 2) in, described reductive agent is the one in sodium borohydride, hydrazine hydrate, inferior sodium phosphate, active metal.
Preferably, in step 2) in, the size of described tin nanoparticles is 30-50nm.
Preferably, in step 3) in, described iron, cobalt reagent are Fe
2(SO
4)
3, Fe (NO
3)
3, FeCl
3, CoCl
2, CoBr
2, Co (NO
3)
2, CoSO
4in one or more.
Preferably, in step 4) in, described cleaning solvent is the one in ethanol, water.Centrifugal rotating speed is between 10000-15000rad/min, and centrifugation time is 10-20 minute.
Major advantage of the present invention comprises:
(1) general tinbase ternary alloy such as, because the quality of other two kinds of elements is comparatively large and the content of tin element is less, AuCuSn
2deng, cause the theoretical specific capacity of material lower.But the present invention successfully prepares tinbase ternary alloy cenotype Fe
1-xco
xsn
5deng material, there is higher theoretical specific capacity, and be the phase that in known tinbase ternary-alloy material, theoretical specific capacity is the highest.
(2) ternary-alloy material successfully prepared of the present invention, due to containing elements such as Fe, Co, effectively alleviate the volumetric expansion of Sn metal among the process of embedding/de-lithium, thus material has good cycle performance.
(3) present invention also offers the method for ternary-alloy material described in the preparation of a kind of wet chemical method, the preparation feedback temperature of described method is lower, and product pattern and size controlled.
Below in conjunction with specific embodiment, set forth the present invention further.Should be understood that these embodiments are only not used in for illustration of the present invention to limit the scope of the invention.The experimental technique of unreceipted actual conditions in the following example, usually conveniently condition, or according to the condition that manufacturer advises.Unless otherwise indicated, otherwise per-cent and number calculate by weight.
Embodiment 1Fe
0.2co
0.8sn
5the preparation of ternary alloy anode material:
Detailed process is as follows:
1) get 2.6g polyvinylpyrrolidone, 60mL Tetraglycol 99 mixes, and is heated to 150 DEG C.At ambient temperature, 1g tin protochloride is fully mixed with 3mL Tetraglycol 99.Then, stannous chloride solution is injected in flask, strong stirring 15 minutes.
2) get 0.5g sodium borohydride, 20mL Tetraglycol 99 fully mixes, and is slowly added drop-wise in flask, the rapid blackening of solution, strong stirring 20 minutes, obtains simple substance tin nanoparticles.
3) 0.08g iron nitrate, 0.12g cobaltous chloride, 3mL Tetraglycol 99 are fully mixed, join in the suspension liquid containing tin nanoparticles, simultaneous temperature is raised to 190 DEG C, strong stirring 1.5 hours.Reaction terminates, slowly cool to room temperature.
4) washing, centrifugal gained nano-metal particle, drying at room temperature 12 hours, obtains Fe
0.2co
0.8sn
5ternary alloy anode material.
Embodiment 2Fe
0.2co
0.8sn
5the structural analysis of ternary alloy anode material:
To Fe prepared by embodiment 1
0.2co
0.8sn
5ternary alloy anode material carries out crystal phase analysis and composition analysis.Fe
0.2co
0.8sn
5ternary alloy crystalline structure is similar to FeSn
5and CoSn
5.The massfraction that the massfraction that the massfraction of Sn is about 90%, Fe is about 2%, Co is about 8%.
As can be seen from Fig. 2 and Fig. 4, alloying pellet is uniform spherical particle, and size is between 30-50nm.Particle surface surround by unbodied zone of oxidation, the thickness of zone of oxidation is 3-4nm.
Embodiment 3Fe
0.2co
0.8sn
5the chemical property analysis of ternary alloy anode material:
The assembling of battery is carried out in the glove box being full of argon gas.Wherein negative pole is lithium electrode, and electrolytic solution is NSC 11801 (EC) and methylcarbonate (DMC) (volume ratio 1:1).Test condition: specific storage is pressed 900mAh/g and calculated, and rate of charge is 0.05C (namely by theoretical calculation of capacity, discharge and recharge respectively needs 20 hours), and charging/discharging voltage scope is 0.05V-1.5V.Experimental result shows, the capacity discharged first can reach 1350mAh/g.
Embodiment 4Fe
0.5co
0.5sn
5the preparation of ternary alloy anode material:
Detailed process is as follows:
1) get 2.6g polyvinylpyrrolidone, 60mL Tetraglycol 99 mixes, and is heated to 150 DEG C.At ambient temperature, 1g tin protochloride is fully mixed with 3mL Tetraglycol 99.Then, stannous chloride solution is injected in flask, strong stirring 15 minutes.
2) get 0.5g sodium borohydride, 20mL Tetraglycol 99 fully mixes, and is slowly added drop-wise in flask, the rapid blackening of solution, strong stirring 20 minutes, obtains simple substance tin nanoparticles.
3) 0.16g iron nitrate, 0.16g cobaltous chloride, 3mL Tetraglycol 99 are fully mixed, join in the suspension liquid containing tin nanoparticles, simultaneous temperature is raised to 190 DEG C, strong stirring 1.5 hours.Reaction terminates, slowly cool to room temperature.
4) at least five washings, centrifugal gained nano-metal particle, drying at room temperature 12 hours, obtains Fe
0.5co
0.5sn
5ternary alloy anode material.
Embodiment 5Fe
0.5co
0.5sn
5the structural analysis of ternary alloy anode material:
To Fe prepared by embodiment 4
0.5co
0.5sn
5ternary alloy anode material carries out crystal phase analysis and composition analysis.Fe
0.5co
0.5sn
5ternary alloy crystalline structure is similar to FeSn
5and CoSn
5, as shown in Figure 1.The massfraction that the massfraction that the massfraction of Sn is about 90%, Fe is about 5%, Co is about 5%, as shown in Figure 3.Experimental result shows: Fe
0.5co
0.5sn
5ternary alloy has similar FeSn
5the structure of binary alloy, it is Tetragonal, belongs to P4/mcc spacer.
Embodiment 6Fe
0.8co
0.2sn
5the preparation of ternary alloy anode material:
1) get 1.6g poly-(2-ethyl-2 oxazoline), 60mL Tetraglycol 99 mixes, and is heated to 140 DEG C.At ambient temperature, 1g tin protochloride is fully mixed with 3mL Tetraglycol 99.Then, stannous chloride solution is injected in flask, strong stirring 15 minutes.
2) get 0.5g hydrazine hydrate, 20mL Tetraglycol 99 fully mixes, and is slowly added drop-wise in flask, the rapid blackening of solution, strong stirring 20 minutes, obtains simple substance tin nanoparticles.
3) 0.16 iron nitrate, 0.08g cobaltous chloride, 3mL Tetraglycol 99 are fully mixed, join in the suspension liquid containing tin nanoparticles, simultaneous temperature is raised to 180 DEG C, strong stirring 1.5 hours.Reaction terminates, slowly cool to room temperature.
4) at least five washings, centrifugal gained nano-metal particle, drying at room temperature 12 hours.
Embodiment 7 ball milled prepares Fe
0.5co
0.5sn
5ternary alloy anode material:
Get Sn:Co:Fe (the molar percentage)=tin particles of 5:0.5:0.5, iron powder, cobalt powder respectively, fully mix.Above-mentioned substance is put into ball grinder, the dehydrated alcohol of quality such as in Axisymmetric Spherical grinding jar, to add.Speed is arranged on 300-800rad/min, abundant ball milling 24-72 hour.Ball milling terminates, and is taken out by gained Fe-Co-Sn powder, tests.
Embodiment 8Fe
0.5co
0.5sn
5the chemical property analysis of ternary alloy anode material:
The assembling of battery is carried out in the glove box being full of argon gas.Wherein negative pole is lithium electrode, and electrolytic solution is NSC 11801 (EC) and methylcarbonate (DMC) (volume ratio 1:1).Test condition: specific storage is pressed 900mAh/g and calculated, and rate of charge is 0.05C (namely by theoretical calculation of capacity, discharge and recharge respectively needs 20 hours), and charging/discharging voltage scope is 0.05V-1.5V.Experimental result is as shown in the table:
| Cycle index | Charge specific capacity (mAh/g) | Specific discharge capacity (mAh/g) |
| 1 | 579.8 | 1153 |
| 2 | 593 | 676.5 |
| 3 | 600.6 | 638.9 |
| 4 | 601.6 | 634.1 |
| 5 | 602.3 | 639.7 |
| 6 | 600.9 | 645.6 |
| 7 | 614.7 | 650.6 |
| 8 | 620.6 | 649.4 |
| 9 | 627.3 | 653.5 |
| 10 | 631.2 | 658.9 |
| 11 | 634.9 | 663.3 |
| 12 | 638.8 | 677.7 |
| 13 | 643.8 | 668.6 |
| 14 | 650.8 | 684.3 |
| 15 | 650 | 683.9 |
| 16 | 659.9 | 701.4 |
| 17 | 654.7 | 688.7 |
| 18 | 646.9 | 695 |
| 19 | 655.9 | 684.7 |
| 20 | 662.1 | 696.6 |
| 21 | 662.7 | 701.5 |
| 22 | 663.6 | 702 |
| 23 | 663.6 | 702.5 |
| 24 | 659.8 | 700.6 |
| 25 | 660 | 695.7 |
| 26 | 659.7 | 696.7 |
| 27 | 657.4 | 693.3 |
| 28 | 656.4 | 693.3 |
| 29 | 653.1 | 690.3 |
| 30 | 654.4 | 693.7 |
Embodiment 9Cu
0.5co
0.5sn
5the preparation of ternary alloy anode material:
Detailed process is as follows:
1) get 1.3g poly-(2-ethyl-2 oxazoline), 55mL Tetraglycol 99 mixes, and is heated to 160 DEG C.At ambient temperature, 1g tin protochloride is fully mixed with 4mL Tetraglycol 99.Then, stannous chloride solution is injected in flask, strong stirring 15 minutes.
2) get 0.8g sodium borohydride, 25mL Tetraglycol 99 fully mixes, and is slowly added drop-wise in flask, the rapid blackening of solution, strong stirring 20 minutes, obtains simple substance tin nanoparticles.
3) 0.2g cupric chloride, 0.16g cobaltous chloride, 5mL Tetraglycol 99 are fully mixed, join in the suspension liquid containing tin nanoparticles, simultaneous temperature is raised to 200 DEG C, strong stirring 1.5 hours.Reaction terminates, slowly cool to room temperature.
4) at least five washings, centrifugal gained nano-metal particle, drying at room temperature 12 hours, obtains Cu
0.5co
0.5sn
5ternary alloy anode material.
Embodiment 10Fe
0.5ni
0.5sn
5the preparation of ternary alloy anode material:
1) get 2.6g polyvinylpyrrolidone, 1.3g gathers (2-ethyl-2 oxazoline), and 60mL Virahol mixes, and is heated to 140 DEG C.At ambient temperature, 1g tin protochloride is fully mixed with 4mL Virahol.Then, stannous chloride solution is injected in flask, strong stirring 15 minutes.
2) get 0.7g sodium borohydride, 20mL Virahol fully mixes, and is slowly added drop-wise in flask, the rapid blackening of solution, strong stirring 20 minutes, obtains simple substance tin nanoparticles.
3) 0.16g iron nitrate, 0.10g nickelous chloride, 4mL Virahol are fully mixed, join in the suspension liquid containing tin nanoparticles, simultaneous temperature is raised to 180 DEG C, strong stirring 1.5 hours.Reaction terminates, slowly cool to room temperature.
4) washing, centrifugal gained nano-metal particle, drying at room temperature 12 hours, obtains Fe
0.5ni
0.5sn
5ternary alloy anode material.
Embodiment 11Cu
0.5ni
0.5sn
5the preparation of ternary alloy anode material:
Detailed process is as follows:
1) get 2.0g polyvinylpyrrolidone, 1.0g gathers (2-ethyl-2 oxazoline), and 30mL ethylene glycol mixes, and is heated to 130 DEG C.At ambient temperature, 0.5g tin protochloride is fully mixed with 2mL ethylene glycol.Then, stannous chloride solution is injected in flask, strong stirring 15 minutes.
2) get 0.5g sodium borohydride, 12mL ethylene glycol fully mixes, and is slowly added drop-wise in flask, the rapid blackening of solution, strong stirring 15 minutes, obtains simple substance tin nanoparticles.
3) 0.1g cupric chloride, 0.08g nickelous chloride, 3mL ethylene glycol are fully mixed, join in the suspension liquid containing tin nanoparticles, simultaneous temperature is raised to 170 DEG C, strong stirring 1.5 hours.Reaction terminates, slowly cool to room temperature.
4) at least five washings, centrifugal gained nano-metal particle, drying at room temperature 12 hours, obtains Cu
0.5ni
0.5sn
5ternary alloy anode material.
The all documents mentioned in the present invention are quoted as a reference all in this application, are just quoted separately as a reference as each section of document.In addition should be understood that those skilled in the art can make various changes or modifications the present invention after having read above-mentioned teachings of the present invention, these equivalent form of values fall within the application's appended claims limited range equally.
Claims (12)
1. a ternary-alloy material, is characterized in that, has the composition be shown below:
A
1-xb
xsn
5formula I
Wherein, A, B are for being selected from lower group: any two kinds in Fe, Ni, Co, Cu, and 0.01≤x≤0.99;
And described ternary-alloy material has Tetragonal.
2. material as claimed in claim 1, it is characterized in that, described A is Fe, B is Co.
3. material as claimed in claim 1, it is characterized in that, in described material, the content of Sn is 60-99wt%, by the total weight of ternary-alloy material.
4. material as claimed in claim 1, it is characterized in that, described material morphology can be any form, comprises powder, block, particle etc.
5. the preparation method of material as claimed in claim 1, it is characterized in that, by being selected from the method preparation of lower group: coprecipitation method, hydrothermal synthesis method, molte-salt synthesis, sol-gel method, sonochemical method, wet chemical method, mechanochemistry method, vacuum arc furnace melting method, planetary type ball-milling method, electrodip process, magnetron sputtering method, plasma reaction method.
6. the preparation method of material as claimed in claim 2, it is characterized in that, described method comprises step:
I () provides Sn ion source solution;
(ii) in the presence of a reducing agent, make the Sn ion reduction in Sn ion source solution, obtain the first solution mixture containing simple substance tin;
(iii) source of iron reagent, cobalt source reagent are mixed with above-mentioned first solution mixture, obtain the second solution mixture;
(iv) under the reducing conditions, make the reducing metal ions in described second solution mixture be simple substance, form the ternary-alloy material shown in formula II;
Fe
1-xco
xsn
5formula II
In formula, 0.01≤x≤0.99.
7. method as claimed in claim 6, it is characterized in that, described Sn ion source solution is prepared by the following method:
In inert environments, Sn presoma is injected in organic solvent, obtains Sn ion source solution;
Preferably, described organic solvent is the organic solvent containing surface stabilizer.
8. the method as described in as arbitrary in claim 6 or 7, is characterized in that, comprise the one or more features being selected from lower group:
Described Sn presoma is tin salt solution; And/or
Described surface stabilizer is selected from lower group: polyvinylpyrrolidone (PVP), cetyl trimethylammonium bromide (CTAB), oleyl amine, poly-(2-ethyl-2 oxazoline) (PEtOx), or its combination; And/or
Described organic solvent is selected from lower group: Virahol, ethylene glycol, diethanolamine, Tetraglycol 99, or its combination; And/or
Described reductive agent is selected from lower group: sodium borohydride, hydrazine hydrate, inferior sodium phosphate, active metal, or its combination; And/or
Described source of iron reagent is molysite or the solution containing ferric ion; And/or
Described cobalt source reagent is cobalt salt or the solution containing cobalt ion.
9. the purposes of ternary-alloy material as claimed in claim 1, is characterized in that, for the preparation of battery cathode active material.
10. a battery cathode active material, is characterized in that, contains ternary-alloy material as claimed in claim 1.
11. 1 kinds of batteries, is characterized in that, described battery contains ternary-alloy material according to claim 1 or battery cathode active material according to claim 10.
12. 1 kinds of goods, is characterized in that, described goods contain ternary-alloy material according to claim 1 or are made up of ternary-alloy material according to claim 1.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310470513.4A CN104577076A (en) | 2013-10-10 | 2013-10-10 | Tin-based ternary alloy negative active material and preparation method thereof |
| PCT/CN2014/088329 WO2015051761A1 (en) | 2013-10-10 | 2014-10-10 | Negative electrode active material of tin-based ternary alloy and preparation method therefor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310470513.4A CN104577076A (en) | 2013-10-10 | 2013-10-10 | Tin-based ternary alloy negative active material and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104577076A true CN104577076A (en) | 2015-04-29 |
Family
ID=52812536
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310470513.4A Pending CN104577076A (en) | 2013-10-10 | 2013-10-10 | Tin-based ternary alloy negative active material and preparation method thereof |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN104577076A (en) |
| WO (1) | WO2015051761A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108172774A (en) * | 2017-11-23 | 2018-06-15 | 浙江大学 | A kind of metastable state kamash alloy material and preparation method thereof |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111029564B (en) * | 2019-12-10 | 2022-11-29 | 河南创力新能源科技股份有限公司 | Preparation method of iron negative electrode material of iron-nickel secondary battery |
| CN116145175B (en) * | 2023-02-22 | 2023-07-21 | 兰州大学 | Electrocatalyst, preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101665883A (en) * | 2009-10-19 | 2010-03-10 | 浙江大学 | Method for preparing nano-porous block of Fe-Sn intermetallic compound |
| CN101692490A (en) * | 2009-10-09 | 2010-04-07 | 宁波职业技术学院 | Preparation method for copper-tin-antimony ternary alloy cathode material of lithium ion battery |
| WO2012174235A1 (en) * | 2011-06-14 | 2012-12-20 | Brookhaven Science Associates, Llc | INTERMETALLIC M-Sn5 (M=Fe, Cu, Co, Ni) COMPOUND AND A METHOD OF SYNTHESIS THEREOF |
| CN103326005A (en) * | 2013-06-27 | 2013-09-25 | 山东建筑大学 | Sn-Ni-Zn ternary alloy soft porous material applied to negative electrode of lithium ion battery and preparation method of Sn-Ni-Zn ternary alloy soft porous material |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1240863C (en) * | 2003-09-18 | 2006-02-08 | 上海交通大学 | Titaniferous cuprum-nickel-stannum spinodal decomposition type anti-friction bearing alloy and preparation method thereof |
| CN102832377A (en) * | 2012-08-17 | 2012-12-19 | 华南理工大学 | Tin-amorphous nickel titanium composite film cathode material and preparation method and application thereof |
-
2013
- 2013-10-10 CN CN201310470513.4A patent/CN104577076A/en active Pending
-
2014
- 2014-10-10 WO PCT/CN2014/088329 patent/WO2015051761A1/en active Application Filing
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101692490A (en) * | 2009-10-09 | 2010-04-07 | 宁波职业技术学院 | Preparation method for copper-tin-antimony ternary alloy cathode material of lithium ion battery |
| CN101665883A (en) * | 2009-10-19 | 2010-03-10 | 浙江大学 | Method for preparing nano-porous block of Fe-Sn intermetallic compound |
| WO2012174235A1 (en) * | 2011-06-14 | 2012-12-20 | Brookhaven Science Associates, Llc | INTERMETALLIC M-Sn5 (M=Fe, Cu, Co, Ni) COMPOUND AND A METHOD OF SYNTHESIS THEREOF |
| CN103326005A (en) * | 2013-06-27 | 2013-09-25 | 山东建筑大学 | Sn-Ni-Zn ternary alloy soft porous material applied to negative electrode of lithium ion battery and preparation method of Sn-Ni-Zn ternary alloy soft porous material |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108172774A (en) * | 2017-11-23 | 2018-06-15 | 浙江大学 | A kind of metastable state kamash alloy material and preparation method thereof |
| CN108172774B (en) * | 2017-11-23 | 2020-12-08 | 浙江大学 | Metastable tin-based alloy material and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2015051761A1 (en) | 2015-04-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6708326B2 (en) | Positive electrode material for sodium secondary batteries | |
| CN102315482B (en) | Lithium secondary battery with metal fluoride as positive electrode material | |
| CN101752555B (en) | Method for preparing lithium ion battery anode material LiFePO4 | |
| CN102299328B (en) | Metal fluoride cathode material of lithium secondary battery and preparation method of cathode material | |
| CN100370644C (en) | Anode material of lithium ion cell and preparation method thereof | |
| CN104157853B (en) | A kind of negative material, its preparation method and application | |
| CN102185143A (en) | Transition metal oxide/ graphene composite material and preparation method thereof | |
| CN106159244A (en) | Lithium battery cathode material, preparation method thereof and lithium ion battery for power | |
| CN102244236A (en) | Method for preparing lithium-enriched cathodic material of lithium ion battery | |
| CN112271279B (en) | Composite positive electrode material, preparation method and application thereof, and lithium ion battery | |
| CN104051725B (en) | A kind of preparation method of high voltage cobalt nickel oxide manganses lithium anode material | |
| CN110336006B (en) | Lithium cobaltate cathode material with high structural stability and preparation method thereof | |
| CN103715406A (en) | Preparation and applications of tin based alloy-carbon composite anode active material | |
| US11362327B2 (en) | Double layer-coated nano-silicon negative electrode material, a method for preparing the same and use thereof | |
| CN106602024A (en) | In-situ surface-modified lithium-rich material and preparation method thereof | |
| CN102315432A (en) | A positive electrode material for C/Li2MSiO4-xNy/C (M=Fe, mn, co) composite lithium ion battery and its preparation method | |
| JP2021048137A (en) | Cathode active material for lithium secondary battery | |
| CN106486657A (en) | A kind of rich lithium material of surface in situ cladding and preparation method thereof | |
| CN115020676A (en) | Sodium ion battery positive electrode material capable of stabilizing oxygen valence change and preparation method thereof | |
| Cheng et al. | Enhanced electrochemical and safe performances of LiNi1/3Co1/3Mn1/3O2 by nano-CeO2 coating via a novel hydrolysis precipitate reaction route | |
| CN102800849B (en) | Transition metal tin compound/graphene composite material and preparation method and application thereof | |
| CN111668464A (en) | Lithium iron phosphate coated nickel-cobalt-aluminum ternary cathode material and preparation method and application thereof | |
| CN104577076A (en) | Tin-based ternary alloy negative active material and preparation method thereof | |
| CN110289407A (en) | A kind of carbon coating cobalt-doping zinc oxide nano material for lithium ion battery | |
| US20140127581A1 (en) | Lithium-Rich Anode Material, Lithium Battery Anode, and Lithium Battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20150429 |