CN109761599A - A kind of preparation method and application of the sub- titanium oxide conductivity ceramics of Magn é li phase - Google Patents
A kind of preparation method and application of the sub- titanium oxide conductivity ceramics of Magn é li phase Download PDFInfo
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Abstract
The invention belongs to electrochemistry and nanometer new material technical field of energy storage, and in particular to a kind of preparation method and applications of the sub- titanium oxide conductivity ceramics of Magn é li phase.The preparation method is that: metallic zinc, nano oxidized titanium powder and halogen sodium salt catalyst are uniformly mixed, are placed in protective gas, control reaction temperature is 915-1550 DEG C, and the reaction time is 5-10 hours, cooling;After reaction, obtained material is spent into water washing, removes wherein halogen sodium salt catalyst, the black blue powders that can be obtained after drying are the sub- titanium oxide conductivity ceramics Ti of Magn é li phasenO2n‑1One of or a variety of mixing.The present invention obtains the sub- titanium oxide conductivity ceramics of Magn é li phase using metallic zinc come reduced nano titanium oxide, and not needing many and diverse post-processing step can be applied in zinc-nickel cell, and production cost is greatly saved, and have apparent economic significance.
Description
Technical field
The invention belongs to electrochemistry and nanometer new material technical field of energy storage, and in particular to a kind of sub- oxidation of Magn é li phase
The preparation method and applications of titanium conductivity ceramics.
Background technique
In order to reduce the use of fossil fuel, the renewable energy such as wind energy, solar energy, tide energy are accelerated development as China
The important link of energy sustainable development strategy.But above-mentioned renewable new energy faced when in use generated output,
The problems such as voltage and frequency fluctuation is big, and the time is uncertain, and continuity is poor is prominent.To guarantee that it is capable of the power supply of continuous-stable,
It needs to develop matched efficient new energy storing technology, and stabilizes the peak-valley difference of power grid using new energy storage technology.For
This, electric supply of Chinese government's important department, military commanding department and Operations Department etc. etc. it is urgent develop it is a kind of completely new
Efficient new energy storing technology or electrochmical power source.
The unique physics of the sub- titanium oxide conductivity ceramics of Magn é li phase, chemical property include especially outstanding chemical stability
And resistance to corrosion, it is highly stable under strong acid and strong base environment, it is more than most industrial common electrode materials;Excellent conduction
Performance can reach 1050S/cm, far super graphite material;It is not easy to reunite without magnetism, it is well dispersed in aqueous electrolyte, make
When for additives for battery, convenient for being mixed with the uniform of other electrode active materials, be conducive to electric current be uniformly distributed and it is wide
Electrochemically stable potential window, stable potential window is 3.0V or more in aqueous solution, this has it in various electrochmical power sources
Good application prospect.The synthetic method feature of the sub- titanium oxide conductivity ceramics of Magn é li phase is predominantly following several at this stage.
1.H2Reduction method
Cardinal principle are as follows: nTiO2+H2→TinO2n-1+H2O
I.e. by TiO2Powder is raw material, at 950-1500 DEG C, leads to hydrogen reducing, obtains the sub- titanium oxide of Magn é li phase and leads
Electroceramics.H2As common reducing agent, there is stronger reproducibility and environment friendly and pollution-free, control gas flow rate in use
Obtain the sub- titanium oxide conductivity ceramics of Magn é li phase.But it as a kind of flammable explosive gas, is using and is needing to infuse constantly in storage and transportation
Meaning uses safe.In addition industrial production H2Price it is higher, it is conductive also to limit the sub- titanium oxide of Magn é li phase to a certain extent
The production cost of ceramics.
2.C reduction method
Cardinal principle are as follows: nTiO2+C→TinO2n-1+CO↑
Medical PVA (PVA) is C precursor, N2Protect lower and TiO2It is reacted at 950-1500 DEG C in tube furnace
The sub- titanium oxide conductivity ceramics of Magn é li phase is obtained, but there are the complete carbon materials of unreacted on surface, it is difficult to remove, such as expect
The sub- titanium oxide conductivity ceramics of carbon-free Magn é li phase also needs further to explore.
3.Ti reduction method
Cardinal principle are as follows: (2n-1) TiO2+Ti→2TinO2n-1
By the Ti and TiO of equimolar amounts2In N after abrading-ball mixing2In protection time and tube furnace at 950-1500 DEG C for a long time
Heat preservation obtains the sub- titanium oxide conductivity ceramics of Magn é li phase.Composite result is preferable, and the predominantly reduction effect of Ti is preferable, and control is anti-
Answer condition that can obtain the sub- titanium oxide conductivity ceramics of Magn é li phase of purity is high.It is unreacted that major defect is how to separate
The high production cost of Ti metal powder and Ti metal.
Therefore, the preparation method for developing a kind of sub- titanium oxide conductivity ceramics of completely new Magn é li phase is explored, it is particularly important.
Summary of the invention
Therefore, technical problem to be solved by the present invention lies in overcome the sub- titanium oxide conductivity ceramics of existing Magn é li phase
Problems present in preparation method.Such as: H2Reduction method raw material is inflammable and explosive at high cost;The sub- oxidation of C reduction method Magn é li phase
There are the complete carbon materials of unreacted on titanium surface, it is difficult to remove;Unreacted Ti metal powder and Ti metal in Ti reduction method
The many and diverse separating treatment of high production cost.A kind of preparation method of sub- titanium oxide conductivity ceramics of completely new Magn é li phase is provided,
Its product may be directly applied in the electrode material of zinc-nickel secondary batteries.
In order to solve the above technical problems, the present invention adopts the following technical scheme:
TiO is restored using Zn the present invention provides a kind of2, the method for preparing the sub- titanium oxide conductivity ceramics of Magn é li phase.
A kind of preparation method of the sub- titanium oxide conductivity ceramics of Magn é li phase of the present invention, includes the following steps:
S1: after evenly mixing by metallic zinc, nano oxidized titanium powder and halogen sodium salt catalyst, it is placed in protective gas
In, be warming up to reaction temperature be 915-1550 DEG C under the conditions of, the reaction time be 5-10 hour, cool down;
After reaction, obtained material is washed with water by S2:S1, wherein halogen sodium salt catalyst is removed, after drying
Obtained black blue powders are the sub- titanium oxide conductivity ceramics Ti of Magn é li phasenO2n-1One of or a variety of mixing.
The preparation method of the sub- titanium oxide conductivity ceramics of Magn é li phase of the present invention, in step S1, the metallic zinc is
Metal zinc or the metal zinc metal sheet after being polished with sand paper;The metallic zinc and the molar ratio of nano-titanium oxide are 1-3:5-9;Institute
The dosage of catalyst is stated as the 0.5-5.0% of metallic zinc and the gross mass of nano-titanium oxide, protective gas is nitrogen or argon
Gas;The nano oxidized titanium powder is less than 500nm;Further, the nano oxidized titanium powder is 300-500nm.
Further, the preparation method of the sub- titanium oxide conductivity ceramics of Magn é li phase of the present invention, the metallic zinc
Molar ratio with the nano-titanium oxide is 1-2:5-8.
It is furthermore preferred that the preparation method of the sub- titanium oxide conductivity ceramics of Magn é li phase of the present invention, Magn é li phase are sub-
Titanium oxide conductivity ceramics TinO2n-1One or more of mixing, wherein n be 3-5 positive integer.
The preparation method of the sub- titanium oxide conductivity ceramics of Magn é li phase of the present invention, the halogen sodium salt catalyst
For sodium chloride.
The preparation method of the sub- titanium oxide conductivity ceramics of Magn é li phase of the present invention, in step S1, the reaction time is
5-9 hours;More excellent is 5-8 hours.
The preparation method of the sub- titanium oxide conductivity ceramics of Magn é li phase of the present invention, the reaction in the step S1
Temperature is 1000-1500 DEG C;It is more preferably 1100-1500 DEG C.
The preparation method of the sub- titanium oxide conductivity ceramics of Magn é li phase of the present invention controls pipe in the step S1
The heating rate of formula furnace is 1-5 DEG C per minute.
The preparation method of the sub- titanium oxide conductivity ceramics of Magn é li phase of the present invention, the sub- oxidation of Magn é li phase obtained
Titanium conductivity ceramics.
A kind of electrode material formula of zinc-nickel secondary batteries, which is characterized in that include Magn é li as claimed in claim 7
Mutually sub- titanium oxide conductivity ceramics.
The technical problem to be solved in the present invention is that overcoming in the prior art, raw material is inflammable and explosive, at high cost, Magn é li phase
There are the complete raw material of unreacted, difficult the problems such as separating for sub- titania surface.A kind of sub- oxygen of completely new Magn é li phase is provided
Change the preparation method of titanium conductivity ceramics, product may be directly applied in the electrode material of zinc-nickel secondary batteries.
Above-mentioned technical proposal of the invention has the advantage that compared to existing technology
1, the preparation method of the sub- titanium oxide conductivity ceramics of a kind of Magn é li phase of the present invention, i.e., by metallic zinc, nano oxygen
Change titanium powder and halogen sodium salt catalyst uniformly mixes, under protective gas protection, being warming up to reaction temperature is 915-1550
DEG C, the reaction time is 5-10 hours, cooling;After reaction, obtained material is washed with water, removes wherein halogen sodium salt catalysis
Agent, the black blue powders that can be obtained after drying are the sub- titanium oxide conductivity ceramics of Magn é li phase.The Zn and TiO of selection2Reduction
Reaction, once feeding intake can be completed whole process.Since the active material of Zinc-nickel battery negative grade piece is exactly ZnO, so being not required to
Complicated post-processing step is wanted to come separation of Zn O and TinO2n-1.Production efficiency is substantially increased, there is apparent economic significance.
2, Zn and TiO that the present invention selects during the preparation process2The sub- titanium oxide conduction of reduction reaction preparation Magn é li phase
Ceramics avoid H2Reduction method raw material is inflammable and explosive at high cost;That there are unreacteds is complete for the sub- titania surface of C reduction method Magn é li phase
Full carbon material, it is difficult to remove and the discharge of toxic gas carbon monoxide;Unreacted Ti metal powder in Ti reduction method, with
And the problems such as many and diverse separating treatment of high production cost of Ti metal.The sub- titanium oxide of Magn é li phase provided by the invention is led
Electroceramics preparation method, simple process, safety are good.
3, Zn and TiO that the present invention selects during the preparation process2The sub- titanium oxide conduction of reduction reaction preparation Magn é li phase
Ceramics, the sub- titanium oxide conductivity ceramics of Magn é li phase is TinO2n-1One or more of mixing, wherein n be 3-5 it is just whole
Number.Electric conductivity is excellent, is more than general carbon material, conductivity is as shown in table 2 below, can achieve 1050Scm-1
4, the preparation method for the sub- titanium oxide conductivity ceramics of Magn é li phase that the present invention refers to, the Magn é li phase of preparation are sub-
Titanium oxide conductivity ceramics is TinO2n-1(wherein 3≤n≤5, n are positive integer), described in metallic zinc with it is described nano oxidized
When the molar ratio of titanium is 1-2:5-8 under suitable condition, the sub- titanium oxide of the good Magn é li phase of crystal habit all can be obtained to lead
Electroceramics TinO2n-1(wherein 3≤n≤5, n are positive integer).
5, the preparation method for the sub- titanium oxide conductivity ceramics of Magn é li phase that the present invention refers to, in the appropriate condition of material ratio
Under, reaction temperature controls within the scope of 1000-1500 DEG C, the sub- titanium oxide conductivity ceramics Ti of Magn é li phasenO2n-1In 3≤n≤5, n
For positive integer, excellent electric conductivity is more than general carbon material, for can effectively keep electrode when Zinc-nickel battery negative additive
Electric current is uniform, inhibits passivation, the deformation of negative electrode material.Reaction time 5-10 hour, the sub- titanium oxide of obtained Magn é li phase are conductive
Ceramics, product crystal habit is good, is used to keep enough in strong alkaline electrolytes when Zinc-nickel battery negative additive
Stability, it is corrosion-resistant.
Detailed description of the invention
Fig. 1: different additive zinc-nickel cell discharge capacity curve graph, 1- comparative example 2 are fabricated to Soft Roll zinc-nickel secondary batteries
Sample, 2- embodiment 4 are fabricated to Soft Roll zinc-nickel secondary batteries sample.
Specific embodiment
In order to which the object, technical solutions and advantages of the present invention are clearer, embodiments of the present invention will be done below
It is described in further detail.The present invention can be embodied in many different forms, and should not be construed as limited to illustrate herein
Embodiment.On the contrary, provide these embodiments so that the disclosure will be thoroughly and completion, make the invention solves technology
Problem, technical solution and advantage are clearer, but the present invention is limited to absolutely not these examples.As described below is only that the present invention is preferable
Embodiment is only used to explain the present invention, and it cannot be construed as a limitation to the scope of the present invention.It should be understood that
It is that any modifications, equivalent replacements and improvementsmade within the spirit and principles of the invention, etc. should be included in the present invention
Protection scope within.Therefore, the scope of protection of the patent of the invention shall be subject to the appended claims.
A kind of specific embodiment of the preparation method of Magn é li phase Asia titanium oxide conductivity ceramics see the table below 1:
1 embodiment reaction condition of table
Embodiment 1:
A kind of sub- titanium oxide conductivity ceramics of Magn é li phase the preparation method comprises the following steps:
The TiO for being 500nm with partial size by the Zn that molar ratio is 1:82Powder and the NaCl catalyst abrading-ball for accounting for gross mass 2%
After mixing, being placed in tube furnace and controlling heating rate under nitrogen protection is 3-4 DEG C/Min, after reacting 9 hours at 1100 DEG C
It takes out, catalyst is washed with deionized water, the sub- titanium oxide conductivity ceramics Ti of Magn é li phase can be obtained after dryingnO2n-1Wherein 3
≤ n≤5, n are positive integer.
Product obtained is black-and-blue crystal, and partial size is shown as 600- after being scanned tunnel microscope (SEM) test
700nm.X-RAY powder diffraction analysis (XRD), which is shown at 26.4 ° 29.6 ° 36.2 ° 55.1 ° of 2 θ=20.8 ° of the angle of diffraction, to be occurred
Significant characteristic peak, characteristic peak starts to become apparent and relatively sharp at 2 θ=20.8 °, illustrate that wherein Magn é li phase Asia aoxidizes
Titanium conductivity ceramics TinO2n-1(wherein 3≤n≤5, n are positive integer) content increases, and crystal habit improves.This explanation is suitably mentioning
The corresponding reaction time can be reduced under conditions of high-temperature, and obtains relatively good product.
Embodiment 2:
A kind of preparation method of the sub- titanium oxide conductivity ceramics of Magn é li phase:
The TiO for being 500nm with partial size by the Zn that molar ratio is 2:52Powder and the NaCl catalyst abrading-ball for accounting for gross mass 3%
After mixing, being placed in tube furnace and controlling heating rate under nitrogen protection is 3-4 DEG C/Min, after reacting 8 hours at 1200 DEG C
It takes out, the catalyst being washed with deionized water, the sub- titanium oxide conductivity ceramics Ti of Magn é li phase can be obtained after dryingnO2n-1Wherein
3≤n≤5, n are positive integer.
It is black-and-blue crystal that product, which is made, and partial size is shown as 600- after being scanned tunnel microscope (SEM) test
700nm.X-RAY powder diffraction analysis (XRD), which is shown at 26.4 ° 29.6 ° 36.2 ° 55.1 ° of 2 θ=20.8 ° of the angle of diffraction, to be occurred
Significant characteristic peak, and characteristic peak starts to become apparent and relatively sharp at 2 θ=20.8 °, illustrate wherein Magn é li phase Asia oxygen
Change titanium conductivity ceramics TinO2n-1(wherein 3≤n≤5, n are positive integer) content increases, and crystal habit improves.
Embodiment 3:
A kind of preparation method of the sub- titanium oxide conductivity ceramics of Magn é li phase:
The TiO for being 500nm with partial size by the Zn that molar ratio is 2:92Powder is ground with 4% or more NaCl catalyst of gross mass is accounted for
After ball mixing, it is placed in tube furnace and controls 5 DEG C/Min of heating rate under nitrogen protection, taken after being reacted 7 hours at 1300 DEG C
Out, catalyst is washed with deionized water, the sub- titanium oxide conductivity ceramics Ti of Magn é li phase can be obtained after dryingnO2n-1Wherein 3≤n
≤ 5, n are positive integer.
Product obtained is black-and-blue crystal, and partial size is shown as 550- after being scanned tunnel microscope (SEM) test
650nm.X-RAY powder diffraction analysis (XRD), which is shown at 26.4 ° 29.6 ° 36.2 ° 55.1 ° of 2 θ=20.8 ° of the angle of diffraction, to be occurred
Significant characteristic peak, and characteristic peak is sharp at 2 θ=20.8 °, illustrates the wherein sub- titanium oxide conductivity ceramics of Magn é li phase
TinO2n-1(wherein 3≤n≤5, n are positive integer) content obviously increases, and crystal habit is good.
Embodiment 4:
A kind of preparation method of the sub- titanium oxide conductivity ceramics of Magn é li phase:
The TiO for being 500nm with partial size by the Zn that molar ratio is 1:72Powder is mixed with gross mass 5%NaCl catalyst abrading-ball is accounted for
It after conjunction, is placed in tube furnace and controls 5 DEG C/Min of heating rate under nitrogen protection, taken after being reacted 6 hours or more at 1400 DEG C
Out, catalyst is washed with deionized water, the sub- titanium oxide conductivity ceramics Ti of Magn é li phase can be obtained after dryingnO2n-1Wherein 3≤n
≤ 5, n are positive integer.
The product of system is black-and-blue crystal, and partial size is shown as 550- after being scanned tunnel microscope (SEM) test
650nm.X-RAY powder diffraction analysis (XRD), which is shown at 26.4 ° 29.6 ° 36.2 ° 55.1 ° of 2 θ=20.8 ° of the angle of diffraction, to be occurred
Significant characteristic peak, and characteristic peak is sharp at 2 θ=20.8 °, illustrates the wherein sub- titanium oxide conductivity ceramics of Magn é li phase
TinO2n-1(wherein 3≤n≤5, n are positive integer) content obviously increases, and crystal habit is good.
Embodiment 5:
A kind of sub- titanium oxide conductivity ceramics of Magn é li phase the preparation method comprises the following steps:
The TiO for being 500nm with partial size by the Zn that molar ratio is 1:62Powder is mixed with gross mass 2%NaCl catalyst abrading-ball is accounted for
It after conjunction, is placed in tube furnace and controls 3-4 DEG C of heating rate/Min under nitrogen protection, taken out after being reacted 5 hours at 1550 DEG C,
Catalyst is washed with deionized water, the sub- titanium oxide conductivity ceramics Ti of Magn é li phase can be obtained after dryingnO2n-1Wherein 3≤n≤
5, n be positive integer.
Product obtained is black-and-blue crystal, and partial size is shown as 600- after being scanned tunnel microscope (SEM) test
700nm.X-RAY powder diffraction analysis (XRD), which is shown at 26.4 ° 29.6 ° 36.2 ° 55.1 ° of 2 θ=20.8 ° of the angle of diffraction, to be occurred
Significant characteristic peak, but characteristic peak is sharply obvious at 2 θ=20.8 °, illustrates that the reaction is good and the sub- titanium oxide of Magn é li phase
Conductivity ceramics TinO2n-1(wherein 3≤n≤5, n are positive integer) crystal habit is good.
Comparative example 1:
A kind of sub- titanium oxide conductivity ceramics of Magn é li phase the preparation method comprises the following steps:
The TiO for being 500nm with partial size by the Zn that molar ratio is 1:52Powder is mixed with gross mass 1%NaCl catalyst abrading-ball is accounted for
After conjunction, it is placed in tube furnace control heating 1-2 DEG C/Min of speed under nitrogen protection, takes out, uses after being reacted 12 hours at 900 DEG C
Deionized water washes off water-soluble catalyst, and product can be obtained after drying.
Product obtained is whole white particles, with by the reactant and indistinction before the above process, is shown at this
Under part, which can not be carried out.
Comparative example 2
A kind of preparation method of the sub- titanium oxide conductivity ceramics of Magn é li phase:
Ask molar ratio to the TiO that Zn and partial size for 1:7 are 500nm2Powder and account for gross mass 5%NaCl catalyst abrading-ball
It after mixing, is placed in tube furnace and controls 5 DEG C/Min of heating rate under nitrogen protection, after being reacted 4 hours or more at 1600 DEG C
It takes out, catalyst is washed with deionized water, the sub- titanium oxide conductivity ceramics Ti of Magn é li phase can be obtained after dryingnO2n-1。
Product obtained is black crystals, and partial size is shown after being scanned tunnel microscope (SEM) test are as follows: 600-
800nm.X-RAY powder diffraction analysis (XRD) shows the sub- titanium oxide conductivity ceramics Ti of Magn é li phasenO2n-1Wherein 3≤n≤5, n
For positive integer, there is characteristic diffraction peak for 26.4 ° 29.6 ° 36.2 ° 55.1 ° in 2 θ=20.8 ° of the angle of diffraction, the feature of the black crystals
Diffraction maximum all moves to right, gentle in 2 θ=25.5 ° peak shapes, illustrates that product has part amorphous state;There is feature at 2 θ=39.1 °
There is metal Ti in peak explanation, reactant over reduction;And there is high peak at 56.1 ° of 2 θ=54.4 °, illustrate it
The sub- titanium oxide conductivity ceramics Ti of Magn é li phasenO2n-1Wherein n >=5 are not target products.
TinO2n-1Conductivity it is as shown in table 2 below, by Ti known to following tablenO2n-1Wherein when n >=5, electric conductivity is significantly reduced.
2 difference n value Asia titanium oxide Ti of tablenO2n-1Conductivity
TinO2n-1 | Conductivity (Scm-1) |
Ti3O5 | 630 |
Ti4O7 | 1050 |
Ti5O9 | 631 |
Ti6O11 | 63 |
Ti8O15 | 25 |
By embodiment 1-6 and comparative example 1-2, experiment effect comparison is it can be seen that the Magn é li phase Asia that the present invention refers to
Titanium oxide conductivity ceramics TinO2n-1Preparation method, described in metallic zinc and the molar ratio of the nano-titanium oxide be 1-2:
When 5-8 under suitable condition, the sub- titanium oxide conductivity ceramics Ti of the good Magn é li phase of crystal habit all can be obtainednO2n-1(its
In 3≤n≤5, n is positive integer).Under conditions of material ratio is appropriate, temperature is the sub- titanium oxide conductivity ceramics of control Magn é li phase
TinO2n-1The key factor of middle n, reaction time are the key factors for controlling product crystal habit.Reaction temperature is 1000-1500
DEG C when, available target product, and in this section, the appropriate temperature that increases can reduce the reaction time.Reaction temperature is 900
DEG C when the reaction carry out slowly, long-time react after raw material unreacted;Reaction temperature is 1600 DEG C or more, when obtain
The sub- titanium oxide conductivity ceramics Ti of Magn é li phasenO2n-1Its n >=5, electric conductivity is very poor, is not suitable for zinc-nickel secondary batteries.
Embodiment 7:
The electrode material composite of zinc-nickel secondary batteries:
Product prepared by comparative selection example 2, according to Magn é li phase Asia titanium oxide conductivity ceramics 10%, conductive black 5%,
60% ptfe emulsion 5% of binder, the ratio of zinc and zinc oxide mix 80%, be not added other additives be fabricated to it is soft
Zinc covering nickel secondary batteries sample 1.
The product that selection example 3 is made, also according to the sub- titanium oxide conductivity ceramics 10% of Magn é li phase, conductive black
5%, the production of other additives is not added in 60% ptfe emulsion 5% of binder, the ratio of zinc and zinc oxide mix 80%
At Soft Roll zinc-nickel secondary batteries sample 2.
We use CT2001A to prepared battery after overactivation, and (Wuhan City is blue for the blue electric battery performance detection system of 5V10mA
Electronics limited liability company) test its discharge capacity and cycle performance.Constant current charge-discharge, charge pressure limiting 2.0V, and electric discharge is eventually
Press 1.2V, test loop 200 times.Its cycle performance is as shown in Figure 1.
Shown by Fig. 1 it can be concluded that, soft-package battery 1 made by the sample made as comparative example 2, cycle performance is poor, with
The made battery of blank zinc oxide is without too big difference;Its cycle performance of soft-package battery 2 made by the sample made as embodiment 3 is good
Good, capacity keeps stablizing, without rapid decay.Main cause is the wherein sub- oxidation of its Magn é li phase of the made sample of comparative example 2
Titanium conductivity ceramics TinO2n-1Wherein n >=5, electric conductivity are substantially reduced, and crystal habit is poor, cannot keep Zinc-nickel battery negative material
The uniformity of electric current in material, so as to cause the passivation of negative electrode material zinc, deformation and the formation of dendrite cause significantly declining for capacity
Subtract.The sub- titanium oxide conductivity ceramics Ti of its Magn é li phase of the sample as prepared by embodiment 3nO2n-1(wherein 3≤n≤5, n are positive whole
Number), electric conductivity is good, can have the uniformity for keeping electric current in negative electrode material in zinc-nickel cell, to inhibit the kind of negative electrode material
Kind problem, keeps capacity to stablize, unattenuated.
Obviously, above-described embodiment be only be clearly to illustrate example, and do not limit the embodiments.It is right
For those of ordinary skill in the art, can also make on the basis of the above description it is other it is various forms of variation or
It changes.There is no necessity and possibility to exhaust all the enbodiments.And thus amplify out it is obvious variation or
Person changes still within the protection scope of the invention.
Claims (8)
1. a kind of preparation method of the sub- titanium oxide conductivity ceramics of Magn é li phase, which comprises the steps of:
S1: after evenly mixing by metallic zinc, nano oxidized titanium powder and halogen sodium salt catalyst, being placed in protective gas, rises
Under the conditions of temperature to reaction temperature is 915-1550 DEG C, the reaction time is 5-10 hours, cooling;
After reaction, obtained material is washed with water by S2:S1, removes wherein catalyst, and what be can be obtained after drying is black-and-blue
Powder is the sub- titanium oxide conductivity ceramics Ti of Magn é li phasenO2n-1One of or a variety of mixing.
2. the preparation method of the sub- titanium oxide conductivity ceramics of Magn é li phase according to claim 1, which is characterized in that step
In rapid S1, metal zinc metal sheet of the metallic zinc for metal zinc or after being polished with sand paper;The metallic zinc and nano-titanium oxide
Molar ratio be 1-3:5-9;The dosage of the catalyst is the 0.5-5.0% of the gross mass of metallic zinc and nano-titanium oxide,
Protective gas is nitrogen or argon gas.
3. the preparation method of the sub- titanium oxide conductivity ceramics of Magn é li phase according to claim 1, which is characterized in that institute
The molar ratio of the metallic zinc and the nano-titanium oxide stated is 1-2:5-8.
4. the preparation method of the sub- titanium oxide conductivity ceramics of Magn é li phase according to claim 1, which is characterized in that
The sub- titanium oxide conductivity ceramics Ti of Magn é li phasenO2n-1One or more of mixing, wherein n be 3-5 positive integer.
5. the preparation method of the sub- titanium oxide conductivity ceramics of Magn é li phase according to claim 1, which is characterized in that institute
The halogen sodium salt catalyst stated is sodium chloride.
6. the preparation method of -5 any sub- titanium oxide conductivity ceramics of the Magn é li phase, feature exist according to claim 1
In in step S1, the reaction time is 5-9 hours;In the step S1, the heating rate of heating is 1-5 DEG C per minute;It is described
Reaction temperature in step S1 is 1000-1500 DEG C.
7. a kind of preparation method of the sub- titanium oxide conductivity ceramics of any one of claim 1-8 Magn é li phase is prepared
The sub- titanium oxide conductivity ceramics of Magn é li phase.
8. a kind of electrode material formula of zinc-nickel secondary batteries, which is characterized in that include Magn é li as claimed in claim 7
Mutually sub- titanium oxide conductivity ceramics.
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CN111525133A (en) * | 2020-03-25 | 2020-08-11 | 眉山顺应动力电池材料有限公司 | Composite conductive agent, lithium ion positive electrode material prepared from composite conductive agent and lithium ion battery |
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CN113979742A (en) * | 2021-11-30 | 2022-01-28 | 松山湖材料实验室 | Magneli phase titanium suboxide ceramic, preparation method thereof and inert electrode |
CN115947614A (en) * | 2022-06-09 | 2023-04-11 | 松山湖材料实验室 | Titanium suboxide ceramic electrode, preparation method and application thereof and electrical equipment |
CN115947614B (en) * | 2022-06-09 | 2024-05-03 | 松山湖材料实验室 | Titanium dioxide ceramic electrode, preparation method and application thereof, and electric equipment |
CN116478560A (en) * | 2023-03-24 | 2023-07-25 | 瑞彩科技股份有限公司 | Black pearlescent pigment and preparation method thereof |
CN116409816A (en) * | 2023-04-28 | 2023-07-11 | 深圳市颐禾科技有限公司 | Preparation method of high-purity nano magneli Xiang Ya titanium oxide |
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