CN104795561B - A kind of nickeliferous oxide anode material of stratiform O3 phase and its preparation method and application - Google Patents
A kind of nickeliferous oxide anode material of stratiform O3 phase and its preparation method and application Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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- 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
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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- H—ELECTRICITY
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- 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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a kind of nickeliferous oxide anode material of stratiform O3 phase and its preparation method and application, the materials chemistry general formulas are as follows: NaxAaNibTicO2‑δ；Ni, Mn and A form octahedral structure with six oxygen atoms of arest neighbors respectively, and are total to side arrangement and constitute transition metal layer；Six oxygen atoms in two layers of transition metal layer form octahedral structure, alkali metal ion Na+Between every two layers of transition metal layer, octahedral site is occupied；A is Li+、Mg2+、B3+、Cu2+、Zn2+、Co3+、Al3+、V3+、Fe3+、Mn3+、Mn4+One of or it is a variety of；The relationship of x, a, b, c, δ and m meet x+ma+2b+4c=2 (2- δ), a+b+c=1；Wherein, 0.75 < x < 1,0 < a < 0.6,0 <b < 0.5,0 < c < 0.6, -0.05 < δ < 0.05.
Description
Technical field
The present invention relates to field of material technology more particularly to a kind of nickeliferous oxide anode material of stratiform O3 phase and its preparations
Method and purposes.
Background technique
At present as the reproducible clean energy resource such as solar energy, wind energy has largely used, but if it is this electric energy is straight
Input power grid is connect, very big impact can be brought to power grid.Thus it is possible to measure conversion and storage has become wherein critical issue.With
And the problem come is how to modulate this electric energy changed over time of storage.Electrochemical energy storage can be converted electrical energy into efficiently
It can be carried out storage at chemistry, and be then converted into stable electric power output.Therefore develop cheap, safety, high capacity, good rate capability,
The suitable secondary cell of voltage range causes the extensive research of people.Lithium ion battery has high energy density, high work
Make voltage, stable circulation, and be widely used, small household electrical appliance are applied to high energy density, powerful
Application apparatus, such as electric car, national grid.However, lithium resource is limited, and it is expensive, so that battery cost increases.And with
Lithium is compared, and rich content of the sodium in the earth's crust, exploitation purification are simple, low in cost, cathode can be used cheaper aluminium foil and make
For collector, much performances similar to lithium are shown in chemical property and its memory mechanism is similar to lithium.Therefore, develop
The secondary research interest for causing people again as effective storage equipment of sodium ion.
Currently, sodium ion battery electrode material receives extensive research, and report a large amount of sodium-ion battery just
Pole material.It is concentrated mainly on the oxide and phosphate two parts of transition metal.Transition metal specifically includes that cobalt, nickel, manganese, chromium,
Vanadium, iron.Vanadium and chromium are toxic elements, big to human body and environmental hazard.Na in the oxidexCoO2It is to be used in sodium ion earliest
Positive electrode in secondary cell, but cobalt is expensive, so as to cause battery increased costs, and current potential 2.2-3.8V it
Between, average potential is lower.Although manganese is cheap, rich content in nature, in the oxide containing pure manganese, one
As manganic Jahn-Teller effect it is obvious.Na0.44MnO2First week charging capacity is relatively low, only 45mAh/g.And it is another
The oxide NaMnO of manganese2Although capacity is relatively high, it is extremely unstable in air.Therefore sodium ion secondary battery is realized
Functionization, positive electrode also needs new research and probe, finds that specific capacity is high, and coulombic efficiency is high, cheap electrode material
Material.
Summary of the invention
The present invention provides a kind of nickeliferous oxide anode material of stratiform O3 phase and its preparation method and application, which has
Stratiform O3 phase structure, capacity is higher, voltage range is suitable, relative inexpensiveness, first all coulombic efficiency height, and this positive material
Material can be stabilized in air, can be used for solar power generation, wind-power electricity generation, smart grid peak regulation, distribution power station, standby
The extensive energy storage device of power supply or communication base station.
In a first aspect, the embodiment of the invention provides a kind of nickeliferous oxide anode material of stratiform O3 phase, layered oxygen
The chemical general formula of compound material are as follows: NaxAaNibTicO2-δ；
Wherein, Ni, Ti are transition metal element, and A is that substituted element is doped to transition metal position；Ni, Mn and A points
Octahedral structure is not formed with six oxygen atoms of arest neighbors, multiple octahedral structures are total to side arrangement and constitute transition metal
Layer；Six oxygen atoms in two layers of transition metal layer form octahedral structure, alkali metal ion Na+Positioned at every two layers transition
Between metal layer, octahedral site is occupied；The A is Li+、Mg2+、B3+、Cu2+、Zn2+、Co3+、Al3+、V3+、Fe3+、Mn3+、Mn4+
One of or it is a variety of；The valent state of the A is m, the x, a, and b, c, the relationship between δ and m meets x+ma+2b+4c=2
(2- δ), and meet a+b+c=1；Wherein, 0.75 < x < 1,0 < a < 0.6,0 <b < 0.5,0 < c < 0.6, -0.05 < δ < 0.05.
Optionally, in the chemical general formula NaxAaNibTicO2-δIn, preferably 0.8≤x < 1,0.01≤a < 0.5,0.2≤b <
0.5,0 < c < 0.5, -0.02 < δ < 0.02.Second aspect, the embodiment of the invention provides a kind of nickeliferous oxide anode materials
Preparation method, the method are solid phase method, comprising:
By the doping gold of the carbonate containing sodium of stoichiometry 102wt%~105wt% of required sodium and required stoichiometry
The oxide of category and the oxide of A are mixed according to the stoichiometric ratio of positive active material, and precursor powder is obtained after grinding uniformly；
The A is Li+、Mg2+、B3+、Cu2+、Zn2+、Co3+、Al3+、V3+、Fe3+、Mn3+、Mn4+One of or it is a variety of；
Gained precursor powder is placed in crucible, it is small that 5~24 are heat-treated in 900 DEG C~1000 DEG C of air atmosphere
When, grinding obtains layered oxide material.
Second aspect, the embodiment of the invention provides a kind of preparation method of nickeliferous oxide anode material, the methods
For sol-gel method, comprising:
By the nickel of the acetate of the sodium ion of stoichiometry 102wt%~105wt% of required sodium and required stoichiometry
Nitrate, butyl titanate and A nitrate be dissolved in dehydrated alcohol or deionized water respectively, and citric acid is added and is formed
Aqueous precursor gel；The A is Li+、Mg2+、B3+、Cu2+、Zn2+、Co3+、Al3+、V3+、Fe3+、Mn3+、Mn4+One of or it is a variety of；
The aqueous precursor gel is placed in crucible, under 250 DEG C~500 DEG C of air atmosphere, is pre-processed 2~6 hours,
Obtain pretreatment powder；
The pretreatment powder is heat-treated 5~20 hours at 800 DEG C~1000 DEG C, grinds, obtains layered oxygen
Compound material.
Fourth aspect, the embodiment of the invention provides a kind of anode pole piece of sodium ion secondary battery, the anode pole piece
Include:
Collector, the conductive additive coated on the collector, binder and as described in above-mentioned first aspect
Nickeliferous oxide anode material.
Optionally, the conductive additive includes: that carbon black, acetylene black, graphite powder, carbon nanotube, graphite are one of dilute
Or it is a variety of.
Optionally, the binder includes:
Kynoar PVDF, polytetrafluoroethylene PTFE, sodium alginate, sodium carboxymethylcellulose CMC, styrene butadiene rubber sbr
Or one or more solution in N-Methyl pyrrolidone NMP.
Optionally, the collector includes: aluminium foil, nickel screen, titanium net, stainless (steel) wire, any one in nickel foam.
5th aspect, the embodiment of the invention provides a kind of sodium ions including anode pole piece described in above-mentioned fourth aspect
Secondary cell.
6th aspect, the bright embodiment of this law provide the use of sodium ion secondary battery described in above-mentioned 5th aspect of one kind
On the way, the sodium ion secondary battery for solar power generation, wind-power electricity generation, smart grid peak regulation, distribution power station, backup power supply or
The extensive energy storage device of communication base station.
The nickeliferous oxide anode material of stratiform O3 phase provided in an embodiment of the present invention has stratiform O3 phase structure, in air
In can be stabilized, can be applied in sodium ion secondary battery, using the nickeliferous oxide anode of stratiform O3 phase of the invention
The sodium ion secondary battery of material, capacity is higher, voltage range is suitable, relative inexpensiveness, first all coulombic efficiency height, Ke Yiyong
It is set in the extensive energy storage of solar power generation, wind-power electricity generation, smart grid peak regulation, distribution power station, backup power supply or communication base station
It is standby.
Detailed description of the invention
Below by drawings and examples, the technical solution of the embodiment of the present invention is described in further detail.
Fig. 1 is a kind of X-ray diffraction for nickeliferous oxide anode material of stratiform O3 phase that the embodiment of the present invention 1 provides
(XRD) map；
Fig. 2 is a kind of SEM figure for nickeliferous oxide anode material of stratiform O3 phase that the embodiment of the present invention 1 provides；
Fig. 3 is a kind of crystal structure figure for nickeliferous oxide anode material of stratiform O3 phase that the embodiment of the present invention 1 provides；
Fig. 4 is a kind of preparation method process for nickeliferous oxide anode material of stratiform O3 phase that the embodiment of the present invention 2 provides
Figure；
Fig. 5 is a kind of preparation method process for nickeliferous oxide anode material of stratiform O3 phase that the embodiment of the present invention 3 provides
Figure；
Fig. 6 is a kind of charging and discharging curve figure for sodium-ion battery that the embodiment of the present invention 4 provides；
Fig. 7 is a kind of charging and discharging curve figure for sodium-ion battery that the embodiment of the present invention 5 provides；
Fig. 8 is a kind of charging and discharging curve figure for sodium-ion battery that the embodiment of the present invention 6 provides；
Fig. 9 is a kind of charging and discharging curve figure for sodium-ion battery that the embodiment of the present invention 7 provides；
Figure 10 is a kind of charging and discharging curve figure for sodium-ion battery that the embodiment of the present invention 8 provides；
Figure 11 is a kind of charging and discharging curve figure for sodium-ion battery that the embodiment of the present invention 9 provides；
Figure 12 is a kind of charging and discharging curve figure for sodium-ion battery that the embodiment of the present invention 10 provides.
Specific embodiment
Below with reference to embodiment, the present invention is further described in detail, but is not intended to limit guarantor of the invention
Protect range.
Embodiment 1
The embodiment of the present invention 1 provides a kind of nickeliferous oxide anode material of stratiform O3 phase, chemical general formula are as follows:
NaxAaNibTicO2-δ；
Wherein, Ni, Ti are transition metal element, and A is that substituted element is doped to transition metal position；The A is Li+、Mg2+、B3+、Cu2+、Zn2+、Co3+、Al3+、V3+、Fe3+、Mn3+、Mn4+One of or it is a variety of；The valent state of the A is m,
The x, a, b, c, the relationship between δ and m meets x+ma+2b+4c=2 (2- δ), and meets a+b+c=1；Wherein, 0.75 < x
< 1,0 < a < 0.6,0 <b < 0.5,0 < c < 0.6, -0.05 < δ < 0.05.
In NaxAaNibTicO2-δStructure in, Ni, Mn and A form octahedra knot with six oxygen atoms of arest neighbors respectively
Structure, multiple octahedral structures are total to side arrangement and constitute transition metal layer；Six oxygen atoms in two layers of transition metal layer are formed
Octahedral structure, alkali metal ion Na+Between every two layers transition metal layer, octahedral site is occupied, to be formed
Stratiform O3 phase structure.
In the following, with Na0.90Mn0.01Ni0.45Ti0.54O2For to the structure of the layered nickeliferous oxide anode material of O3 phase
It is described in detail.
Fig. 1 show Na0.90Mn0.01Ni0.45Ti0.54O2X-ray diffraction (X-ray diffraction, XRD) map,
The Na provided in this embodiment it can be seen from XRD spectrum0.90Mn0.01Ni0.45Ti0.54O2For stratiform O3 phase structure.
Fig. 2 show Na0.90Mn0.01Ni0.45Ti0.54O2Scanning electron microscope (SEM) figure；Fig. 3 is shown
Na0.90Mn0.01Ni0.45Ti0.54O2Space structure schematic diagram.
The nickeliferous oxide anode material of stratiform O3 phase provided in an embodiment of the present invention has stratiform O3 phase structure, in air
In can be stabilized, can be applied in sodium ion secondary battery as positive electrode active materials.
Embodiment 2
A kind of preparation method of nickeliferous oxide anode material of stratiform O3 phase, specially solid phase method are present embodiments provided,
As shown in Figure 4, comprising:
Step 401, by the carbonate containing sodium of stoichiometry 102wt%~105wt% of required sodium and required stoichiometry
Doping metals oxide and A oxide according to positive active material stoichiometric ratio mix, grinding uniformly after before
Drive body powder；
Specifically, the A is Li+、Mg2+、B3+、Cu2+、Zn2+、Co3+、Al3+、V3+、Fe3+、Mn3+、Mn4+One of or
It is a variety of.
Step 402, gained precursor powder is placed in crucible, is heat-treated 5 in 900 DEG C~1000 DEG C of air atmosphere
~24 hours, grinding obtained layered oxide material.
Preparation method provided in this embodiment can be used in preparing the nickeliferous oxygen of stratiform O3 phase described in above-described embodiment 1
Compound positive electrode.Method provided in this embodiment is simple and easy, it is low in cost, may be adapted to apply on a large scale.
Embodiment 3
A kind of preparation method of nickeliferous oxide anode material of stratiform O3 phase is present embodiments provided, specially colloidal sol-is solidifying
Glue method, as shown in Figure 5, comprising:
Step 501, by the acetate and required chemistry of the sodium ion of stoichiometry 102wt%~105wt% of required sodium
The nitrate of the nitrate (such as nickel nitrate) of the nickel of metering, butyl titanate and A is dissolved in dehydrated alcohol or deionized water respectively
In, and citric acid is added and forms aqueous precursor gel；
Specifically, the A is Li+、Mg2+、B3+、Cu2+、Zn2+、Co3+、Al3+、V3+、Fe3+、Mn3+、Mn4+One of or
It is a variety of.
Step 502, the aqueous precursor gel is placed in crucible, under 250 DEG C~500 DEG C of air atmosphere, pretreatment 2
~6 hours, obtain pretreatment powder；
Step 503, the pretreatment powder is heat-treated 5~20 hours at 800 DEG C~1000 DEG C, grinds, obtains institute
State layered oxide material.
Preparation method provided in this embodiment can be used in preparing the nickeliferous oxygen of stratiform O3 phase described in above-described embodiment 1
Compound positive electrode.Method provided in this embodiment is simple and easy, it is low in cost, may be adapted to apply on a large scale.
Illustrate to prepare 1 laminate of embodiment using the method that the above embodiment of the present invention provides with multiple specific examples below
The detailed process of the nickeliferous oxide anode material of O3 phase, and it is applied to the method and battery behavior of secondary cell.
Embodiment 4
The present embodiment prepares active material, specific steps using solid phase method are as follows: by Na2CO3(analysis is pure), NiO, MnO2And
TiO2It stoichiometrically mixes, wherein Na excessive 2%, in the agate mortar mixed grinding half an hour, obtains presoma；Will before
It drives the tabletting of body substance and is transferred to Al2O3In crucible, handled 20 hours under 1000 degrees Celsius in Muffle furnace, gained green ceramic
Piece is polished spare, active material Na as of the invention0.90Mn0.01Ni0.45Ti0.54O2。
Sodium-ion battery is prepared into using above-mentioned active material as positive electrode.Specific steps are as follows: the activity that will be prepared
Substance Na0.90Mn0.01Ni0.45Ti0.54O2Powder and acetylene black, binder Kynoar (PVDF) according to 70:20:10 quality
Than mixing, suitable N-Methyl pyrrolidone (NMP) Solutions Solution is added, grinding forms slurry in the environment of air drying,
Then slurry is evenly applied in current collector aluminum foil, and dry under infrared lamp, is cut into the pole piece of 8 × 8mm.In vacuum condition
Under it is 10 hours dry in 100 DEG C, it is spare to be transferred to glove box immediately.In the glove box for being assemblied in Ar atmosphere of simulated battery into
Row, using metallic sodium piece as to electrode, the NaClO of 1M4/ ethylene carbonate (EC): diethyl carbonate (DEC) solution is as electrolysis
Liquid is assembled into CR2032 button cell.It is tested using constant current charge-discharge mode, electric discharge is 2.5V by voltage, and charging is cut
It is 4.2V to voltage, all tests carry out under C/10 current density.Test result is shown in Fig. 6.It is first week, second respectively
Week, 4th week and the tenth week charge and discharge cycles curve.It can be seen from Fig. 6 that the voltage range of main capacity is in 2.8-4.2V, head
For all charging capacitys up to 118mAh/g, specific discharge capacity 103.5mAh/g, first week coulombic efficiency is about 87.7%, is charged within the tenth week
Specific capacity 107mAh/g, 102 mAh/g of specific discharge capacity.
Embodiment 5
The present embodiment prepares active material, specific steps using solid phase method are as follows: by Na2CO3(analysis is pure), NiO, Mn2O3And
TiO2Stoichiometrically mix, wherein Na content excessive 2%, in the agate mortar mixed grinding half an hour, obtains presoma,
By presoma tabletting and it is transferred to Al2O3In crucible, handled 20 hours under 1000 degrees Celsius in Muffle furnace, the brown toner of gained
Polished spare, the as of the invention active material Na in end0.85Mn0.05Ni0.42Ti0.555O2。
Above-mentioned positive active material is prepared into sodium-ion battery, and carries out electro-chemical test.Its test method and implementation
Example 4 is essentially identical.Test voltage range is 2.5V-4.1V, and test result is shown in Fig. 7.Respectively first week charging curve and first
All discharge curves.It can be seen from Fig. 7 that its first all charging capacity is 98mAh/g, first week discharge capacity is up to 90mAh/g, first week coulomb
Efficiency is about 91.8%.
Embodiment 6
The present embodiment prepares active material, specific steps using solid phase method are as follows: by Na2CO3(analysis is pure), NiO, Co2O3And
TiO2Stoichiometrically mix, wherein sodium content excessive 5%, in the agate mortar mixed grinding half an hour, obtains presoma,
By presoma tabletting and it is transferred to Al2O3In crucible, handled 20 hours under 1000 degrees Celsius in Muffle furnace, the brown toner of gained
Polished spare, the as of the invention active material Na in end0.80Co0.10Ni0.35Ti0.55O2。
Above-mentioned positive active material is prepared into sodium-ion battery, and carries out electro-chemical test.Its test method and implementation
Example 4 is essentially identical, and test voltage range is 2.5V-4.1V, and test result is shown in Fig. 8.Respectively first week charging curve and first
All discharge curves.It can be seen from Fig. 8 that its first all charging capacity is 90mAh/g, first week discharge capacity is up to 86mAh/g, first week coulomb
Efficiency is about 95%.
Embodiment 7
The present embodiment prepares active material, specific steps using solid phase method are as follows: by Na2CO3(analysis is pure), NiO, Fe2O3And
TiO2Stoichiometrically mix, wherein sodium content excessive 2%, in the agate mortar mixed grinding half an hour, obtains presoma,
By presoma tabletting and it is transferred to Al2O3In crucible, handled 20 hours under 1000 degrees Celsius in Muffle furnace, the brown toner of gained
Polished spare, the as of the invention active material Na in end0.75Fe0.12Ni0.315Ti0.565O2。
Above-mentioned positive active material is prepared into sodium-ion battery, and carries out electro-chemical test.Its test method and implementation
Example 4 is essentially identical.Test voltage range is 2.5V-4.1V, and test result is shown in Fig. 9.Respectively first week charging curve and first
All discharge curves.It can be seen from Fig. 9 that its first all charging capacity is 80mAh/g, first week discharge capacity is up to 76mAh/g, first week coulomb
Efficiency is about 95%.
Embodiment 8
The present embodiment prepares active material, specific steps using solid phase method are as follows: by Na2CO3(analysis is pure), NiO, B2O3And
TiO2Stoichiometrically mix, wherein sodium content excessive 2%, in the agate mortar mixed grinding half an hour, obtains presoma,
By presoma tabletting and it is transferred to Al2O3In crucible, handled 20 hours under 1000 degrees Celsius in Muffle furnace, the brown toner of gained
Polished spare, the as of the invention active material Na in end0.95B0.05Ni0.40Ti0.595O2。
Above-mentioned positive active material is prepared into sodium-ion battery, and carries out electro-chemical test.Its test method and implementation
Example 4 is essentially identical.Test voltage range is 2.5V-4.2V, and test result is shown in Figure 10.Respectively first week charging curve and first
All discharge curves.It can be seen from Fig. 10 that its first all charging capacity is 110mAh/g, first week discharge capacity is first up to 102.5mAh/g
All coulombic efficiencies are about 93.1%.
Embodiment 9
The present embodiment prepares active material, specific steps using solid phase method are as follows: by Na2CO3(analysis is pure), NiO, Al2O3And
TiO2Stoichiometrically mix, wherein sodium content excessive 4%, in the agate mortar mixed grinding half an hour, obtains presoma,
By presoma tabletting and it is transferred to Al2O3In crucible, handled 20 hours under 1000 degrees Celsius in Muffle furnace, the brown toner of gained
Polished spare, the as of the invention active material Na in end0.82Al0.08Ni0.42Ti0.50O2。
Above-mentioned positive active material is prepared into sodium-ion battery, and carries out electro-chemical test.Its test method and implementation
Example 4 is essentially identical.Test voltage range is 2.5V-4.2V, and test result is shown in Figure 11.Respectively first week charging curve and first
All discharge curves.It can be seen from Fig. 11 that its first all charging capacity is 90mAh/g, first week discharge capacity is up to 81mAh/g, first Zhou Ku
Logical sequence efficiency is about 90%.
Embodiment 10
The present embodiment prepares active material, specific steps using solid phase method are as follows: by Na2CO3(analysis is pure), NiO, Mn2O3、
Al2O3And TiO2It stoichiometrically mixes, wherein sodium content excessive 2%, in the agate mortar mixed grinding half an hour, obtains
Presoma by presoma tabletting and is transferred to Al2O3It in crucible, is handled 20 hours under 1000 degrees Celsius in Muffle furnace, gained palm fibre
Brown powder is polished spare, active material Na as of the invention0.86Al0.02Mn0.03Ni0.38Ti0.57O2。
Above-mentioned positive active material is prepared into sodium-ion battery, and carries out electro-chemical test.Its test method and implementation
Example 4 is essentially identical.Test voltage range is 2.5V-4.1V, and test result is shown in Figure 12.Respectively first week charging curve and first
All discharge curves.It can be seen from Fig. 12 that its first all charging capacity is 98mAh/g, first week discharge capacity is up to 92mAh/g, first Zhou Ku
Logical sequence efficiency is about 93.8%.
Embodiment 11
The present embodiment prepares active material, specific steps using solid phase method are as follows: by Na2CO3(analysis is pure), Al2O3、NiO、
Mn2O3And TiO2It stoichiometrically mixes, wherein sodium content excessive 2%, in the agate mortar mixed grinding half an hour, obtains
Presoma by presoma tabletting and is transferred to Al2O3In crucible, handled 20 hours under 1000 degrees Celsius in Muffle furnace, gained is green
Toner tailpiece is polished spare, active material Na as of the invention0.85Al0.05Mn0.30Ni0.425Ti0.225O2。
Above-mentioned positive active material is prepared into sodium-ion battery, and carries out charge-discharge test.Its test method and implementation
Example 4 is essentially identical.Test voltage range is 2.5V-4.2V, and test result see the table below 1.
Embodiment 12
The present embodiment prepares active material, specific steps using solid phase method are as follows: by Na2CO3(analysis pure), ZnO, NiO and
TiO2Stoichiometrically mix, wherein sodium content excessive 2%, in the agate mortar mixed grinding half an hour, obtains presoma,
By presoma tabletting and it is transferred to Al2O3In crucible, handled 20 hours under 1000 degrees Celsius in Muffle furnace, gained green powder
Piece is polished spare, active material Na as of the invention0.90Zn0.01Co0.04Ni0.40Ti0.55O2。
Above-mentioned positive active material is prepared into sodium-ion battery, and carries out electro-chemical test.Its test method and implementation
Example 4 is essentially identical.Test voltage range is 2.5V-4.1V, as a result see the table below 1.
Embodiment 13
The present embodiment prepares active material, specific steps using solid phase method are as follows: by Na2CO3(analysis is pure), (MgCO3)4·
Mg(OH)2·5H2O (analysis is pure), NiO and TiO2It stoichiometrically mixes, wherein sodium content excessive 2%, in the agate mortar
Mixed grinding half an hour, presoma is obtained, by presoma tabletting and is transferred to Al2O3In crucible, 1000 degrees Celsius in Muffle furnace
Lower processing 20 hours, gained green flour tailpiece is polished spare, active material as of the invention
Na0.90Mg0.05Ni0.40Ti0.55O2。
Above-mentioned positive active material is prepared into sodium-ion battery, and carries out electro-chemical test.Its test method and implementation
Example 4 is essentially identical.Test voltage range is 2.5V-4.1V, as a result see the table below 1.
Embodiment 14
The present embodiment prepares active material, specific steps using solid phase method are as follows: by Na2CO3(analysis is pure), Li2CO3(analysis
It is pure), NiO and TiO2It stoichiometrically mixes, wherein sodium content excessive 2%, in the agate mortar mixed grinding half an hour, obtains
To presoma, by presoma tabletting and it is transferred to Al2O3In crucible, handled 20 hours under 1000 degrees Celsius in Muffle furnace, gained
Green flour tailpiece is polished spare, active material Na as of the invention0.80Li0.10Ni0.40Ti0.50O1.98。
Above-mentioned positive active material is prepared into sodium-ion battery, and carries out electro-chemical test.Its test method and implementation
Example 4 is essentially identical.Test voltage range is 2.5V-4.2V, as a result see the table below 1.
Embodiment 15
The present embodiment prepares active material, specific steps using solid phase method are as follows: by Na2CO3(analysis is pure), Al2O3, NiO and
TiO2Stoichiometrically mix, wherein sodium content excessive 2%, in the agate mortar mixed grinding half an hour, obtains presoma,
By presoma tabletting and it is transferred to Al2O3In crucible, handled 20 hours under 1000 degrees Celsius in Muffle furnace, gained green powder
Piece is polished spare, active material Na as of the invention0.95Al0.05Co0.05Ni0.40Ti0.50O2。
Above-mentioned positive active material is prepared into sodium-ion battery, and carries out electro-chemical test.Its test method and implementation
Example 4 is essentially identical.Test voltage range is 2.5V-4.2V, as a result see the table below 1.
Embodiment 16
The present embodiment prepares active material, specific steps using solid phase method are as follows: by Na2CO3(analysis is pure), NiO, MnO2And
TiO2Stoichiometrically mix, wherein sodium content excessive 2%, in the agate mortar mixed grinding half an hour, obtains presoma,
By presoma tabletting and it is transferred to Al2O3In crucible, handled 24 hours under 1000 degrees Celsius in Muffle furnace, gained pale green toner
Tailpiece is polished spare, active material Na as of the invention0.92Mn0.04Ni0.46Ti0.50O2。
Above-mentioned positive active material is prepared into sodium-ion battery, and carries out electro-chemical test.Its test method and implementation
Example 4 is essentially identical.Test voltage range is 2.5V-4.2V, as a result see the table below 1.
Embodiment 17
The present embodiment prepares active material, specific steps using solid phase method are as follows: by Na2CO3(analysis is pure), ZnO, NiO,
TiO2And Mn2O3It stoichiometrically mixes, wherein sodium content excessive 2%, in the agate mortar mixed grinding half an hour, obtains
Presoma by presoma tabletting and is transferred to Al2O3In crucible, handled 18 hours under 980 degrees Celsius in Muffle furnace, gained is green
Toner tailpiece is polished spare, active material Na as of the invention0.90Zn0.05Mn0.20Ni0.40Ti0.35O2。
Above-mentioned positive active material is prepared into sodium-ion battery, carries out electro-chemical test.Its test method and embodiment 4
It is essentially identical.Test voltage range is 2.5V-4.2V, as a result see the table below 1.
Embodiment 18
The present embodiment prepares active material, specific steps using solid phase method are as follows: by Na2CO3(analysis is pure), MgO, NiO,
TiO2And Mn2O3It stoichiometrically mixes, wherein sodium content excessive 2%, in the agate mortar mixed grinding half an hour, obtains
Presoma by presoma tabletting and is transferred to Al2O3In crucible, handled 20 hours under 1000 degrees Celsius in Muffle furnace, gained is green
Toner tailpiece is polished spare, active material Na as of the invention0.80Zn0.02Mn0.03Ni0.35Ti0.60O2。
Above-mentioned positive active material is prepared into sodium-ion battery, carries out electro-chemical test.Its test method and embodiment 4
It is essentially identical.Test voltage range is 2.5V-4.2V, as a result see the table below 1.
Embodiment 19
The present embodiment prepares active material, specific steps using solid phase method are as follows: by Na2CO3(analysis is pure), B2O3、NiO、
MnO2And TiO2It stoichiometrically mixes, wherein sodium content excessive 2%, in the agate mortar mixed grinding half an hour, before obtaining
Body is driven, by presoma tabletting and is transferred to Al2O3It in crucible, is handled 20 hours under 1000 degrees Celsius in Muffle furnace, gained green
Sheets of powder is polished spare, active material Na as of the invention0.80B0.04Mn0.08Ni0.38Ti0.50O2。
Above-mentioned positive active material is prepared into sodium-ion battery, and carries out electro-chemical test.Its test method and implementation
Example 4 is essentially identical.Test voltage range is 2.5V-4.2V, as a result see the table below 1.
Table 1
Although above-described embodiment 5-19 is contained with the solid phase method that the application embodiment of the present invention 2 provides to illustrate to prepare stratiform O3 phase
The detailed process of nickel oxide positive electrode, and it is applied to the method and battery behavior of secondary cell, but do not limit
Above-described embodiment 5-19 can only carry out material preparation, those skilled in the art using the solid phase method that the embodiment of the present invention 2 provides
It is readily apparent that, the sol-gel method of the offer of the embodiment of the present invention 3 can be used also to prepare the stratiform of above-described embodiment 5-19
The nickeliferous oxide anode material of O3 phase.
A kind of nickeliferous oxide anode material provided by the invention, has that O3 layer structure, capacity be higher, voltage range is closed
Suitable, relative inexpensiveness, first all coulombic efficiencies are high, and this positive electrode can be stabilized in air.In addition, for
Existing O3 phase material, such as Na content is 1, general formula NaMO2For the material of (wherein M is transition metal element), for
The chemicals that Na is 1, it is often unstable in air.But Na of the Na content less than 1 provided by the inventionxAaNibTicO2-δ
(0.75 < x < 1) can be but stabilized with O3 phase structure, and more stable in air.
The nickeliferous oxide anode material of stratiform O3 phase provided in an embodiment of the present invention has stratiform O3 phase structure, in air
In can be stabilized, can be applied in sodium ion secondary battery, operating voltage range is between 3.0~4.2V, average
Voltage is about 3.4V.Using the sodium ion secondary battery of the nickeliferous oxide anode material of stratiform O3 phase of the invention, capacity is higher,
Voltage range is suitable, relative inexpensiveness, first all coulombic efficiencies are high, can be used for solar power generation, wind-power electricity generation, smart grid
Peak regulation, the extensive energy storage device for being distributed power station, backup power supply or communication base station.
Above-described specific embodiment has carried out further the purpose of the present invention, technical scheme and beneficial effects
It is described in detail, it should be understood that being not intended to limit the present invention the foregoing is merely a specific embodiment of the invention
Protection scope, all within the spirits and principles of the present invention, any modification, equivalent substitution, improvement and etc. done should all include
Within protection scope of the present invention.
Claims (8)
1. a kind of nickeliferous oxide anode material of stratiform O3 phase, which is characterized in that the chemical general formula of the material are as follows:
NaxAaNibTicO2-δ；
Wherein, Ni, Ti are transition metal element, and A is that substituted element is doped to transition metal position；Ni, Ti and A respectively with
Six oxygen atoms of arest neighbors form octahedral structure, and multiple octahedral structures are total to side arrangement and constitute transition metal layer；Two
Six oxygen atoms in layer transition metal layer form octahedral structure, alkali metal ion Na+Positioned at every two layers transition metal
Between layer, octahedral site is occupied；The A is Li+、Mg2+、B3+、Cu2+、Zn2+、Co3+、Al3+、V3+、Fe3+、Mn3+、Mn4+In
It is one or more；The valent state of the A is m, the x, a, and b, c, the relationship between δ and m meets x+ma+2b+4c=2 (2-
δ), and meet a+b+c=1；Wherein, 0.8≤x < 1,0.01≤a < 0.5,0.35≤b < 0.5,0 < c < 0.5, -0.02 < δ <
0.02；The preparation method of the material is selected from one of solid phase method and sol-gel method；
The solid phase method preparation process includes: by the carbonate containing sodium and requiredization of the stoichiometry 102%~105% of required sodium
The oxide of the metal oxide and A of learning Ni, Ti of metering is mixed according to the stoichiometric ratio of positive active material, and grinding is uniform
Precursor powder is obtained afterwards；Gained precursor powder is placed in crucible, is heat-treated 5 in 900 DEG C~1000 DEG C of air atmosphere
~24 hours, grinding obtained layered oxide material；
The sol-gel method preparation process includes: by the acetic acid of the sodium ion of the stoichiometry 102%~105% of required sodium
The nitrate of the nitrate of salt and the nickel of required stoichiometry, butyl titanate and A is dissolved in dehydrated alcohol or deionization respectively
In water, and citric acid is added and forms aqueous precursor gel；The aqueous precursor gel is placed in crucible, in 250 DEG C~500 DEG C of sky
It under gas atmosphere, pre-processes 2~6 hours, obtains pretreatment powder；By the pretreatment powder at 800 DEG C~1000 DEG C at heat
Reason 5~20 hours, grinding, obtains layered oxide material.
2. a kind of preparation method of such as above-mentioned nickeliferous oxide anode material described in claim 1, which is characterized in that the side
Method is solid phase method, comprising:
The metal of the carbonate containing sodium of the stoichiometry 102%~105% of required sodium and Ni, Ti of required stoichiometry are aoxidized
The oxide of object and A are mixed according to the stoichiometric ratio of positive active material, and precursor powder is obtained after grinding uniformly；
Gained precursor powder is placed in crucible, is heat-treated 5~24 hours, grinds in 900 DEG C~1000 DEG C of air atmosphere
Mill, obtains layered oxide material.
3. a kind of preparation method of such as above-mentioned nickeliferous oxide anode material described in claim 1, which is characterized in that the side
Method is sol-gel method, comprising:
By the nitrate of the acetate of the sodium ion of the stoichiometry 102%~105% of required sodium and the nickel of required stoichiometry,
The nitrate of butyl titanate and A are dissolved in dehydrated alcohol or deionized water respectively, and it is solidifying that citric acid formation presoma is added
Glue；
The aqueous precursor gel is placed in crucible, under 250 DEG C~500 DEG C of air atmosphere, pre-processes 2~6 hours, obtains
Pre-process powder；
The pretreatment powder is heat-treated 5~20 hours at 800 DEG C~1000 DEG C, grinds, obtains layered oxide
Material.
4. a kind of anode pole piece of sodium ion secondary battery, which is characterized in that the anode pole piece includes:
Collector, the conductive additive coated on the collector, binder and as above-mentioned described in claim 1 nickeliferous
Oxide anode material.
5. anode pole piece according to claim 4, which is characterized in that the conductive additive include: carbon black, graphite powder,
One of carbon nanotube, graphene are a variety of.
6. anode pole piece according to claim 4, which is characterized in that the binder includes:
Kynoar PVDF, polytetrafluoroethylene PTFE, sodium alginate, sodium carboxymethylcellulose CMC, one in styrene butadiene rubber sbr
Kind or a variety of solution.
7. anode pole piece according to claim 4, which is characterized in that the collector includes: aluminium foil, nickel screen, titanium net, no
Become rusty steel mesh, any one in nickel foam.
8. a kind of sodium ion secondary battery, including the described in any item anode pole pieces of claim 4-7.
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| CN105914354A (en) * | 2016-05-09 | 2016-08-31 | 北京工业大学 | Sodium-rich type titanium matrix layered solid solution electrode material for room-temperature sodium ion battery and preparation method |
| CN107516729B (en) * | 2016-06-17 | 2022-04-08 | 中国科学院上海硅酸盐研究所 | Transition metal layer lithium-containing layered electrode material for symmetrical secondary battery and preparation method and application thereof |
| CN109904386A (en) * | 2017-12-07 | 2019-06-18 | 中国电力科学研究院有限公司 | A kind of stanniferous layered oxide material and its preparation method and application |
| CN112670497A (en) * | 2019-09-27 | 2021-04-16 | 宁德时代新能源科技股份有限公司 | Positive electrode active material for sodium ion battery, battery module, battery pack, and device each made of the active material |
| CN110783525A (en) * | 2019-10-31 | 2020-02-11 | 溧阳中科海钠科技有限责任公司 | Positive electrode additive for sodium ion battery, battery positive electrode, sodium ion battery and application |
| CN111762820A (en) * | 2020-07-14 | 2020-10-13 | 宁夏大学 | Layered manganese-based positive electrode material of sodium-ion battery and preparation method thereof |
| CN114790013B (en) * | 2021-01-26 | 2023-10-13 | 中国科学院物理研究所 | Sodium ion battery positive electrode active material capable of self-supplementing sodium, preparation method and application thereof |
| CN116119730A (en) * | 2021-11-12 | 2023-05-16 | 中国科学院物理研究所 | Oxide composite positive electrode material coated with borate in situ, preparation method and application |
| WO2023230825A1 (en) * | 2022-05-31 | 2023-12-07 | 宁德时代新能源科技股份有限公司 | Layered oxide and preparation method therefor, positive electrode plate, secondary battery, battery module, battery pack and electric device |
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