CN110504443A - Sodium magnesium manganese base layered oxide material, preparation method and the purposes appraised at the current rate with anion - Google Patents
Sodium magnesium manganese base layered oxide material, preparation method and the purposes appraised at the current rate with anion 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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- 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
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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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- 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
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- 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
- Y02E60/16—Mechanical energy storage, e.g. flywheels or pressurised fluids
Abstract
The invention discloses a kind of sodium magnesium manganese base layered oxide material, preparation method and purposes appraised at the current rate with anion, the chemical general formulas of the material are as follows: Naa[MgbMnc]O2+β；A, b, c, β are respectively molar percentage shared by corresponding element；Relationship between them meets b+c=1, and a+b+4c=2 × (2+ β)；Wherein 0.5≤a≤0.85；0.25≤b≤0.425；0.575≤c≤0.75；-0.02≤β≤0.02；The space group of layered oxide material is P63/ mmc or P63/ mcm or R-3m, counter structure are P2 phase or P3 phase.Anion appraises at the current rate positive electrode active materials of the layered oxide material for sodium ion secondary battery, and when first week charging, the oxonium ion in lattice loses electronics, and average valence increases the valence state become between -2 and -1 from -2；When first Zhou Fang electricity, the oxonium ion with higher valence state retrieves electronics, and with going deep into for electric discharge, part manganese ion can obtain electronics, and average valence becomes trivalent from tetravalence；Since second week, oxonium ion and manganese ion can participate in reversible receiving and losing electrons process jointly in charge and discharge process.
Description
Technical field
The present invention relates to field of material technology more particularly to a kind of sodium magnesium manganese base layered oxides to appraise at the current rate with anion
Material, preparation method and purposes.
Background technique
With the development and progress of society, the mankind are increasing to the demand of the energy, but coal, petroleum, natural gas etc. pass
Fossil energy of uniting is since resource is increasingly exhausted, along with city environmental pollution and greenhouse effects problem caused by it are increasingly serious,
Its application is gradually limited by various aspects, therefore the exploitation of sustainable clean energy resource is always the direction of various countries' concern.But it will
During wind energy, solar energy and tide energy etc. are converted into electric energy, these renewable energy limited by natural conditions it is larger, and
Have the characteristics that apparent time discontinuity, spatial distribution inhomogeneities, this electric power controllability for causing them to provide and steady
It is qualitative poor, power grid use cannot be directly inputted.Therefore, only mating high performance large-scale energy storage system, solves to send out with this
Electricity and the time difference contradiction of electricity consumption adjust electric power quality, just can ensure that electric system reliable power supply.Currently China's energy is sustainable
Development is more urgent to extensive energy storage technology demand, while this is also the research hotspot of countries in the world.
Current existing energy storage mode is divided into physics energy storage and chemical energy storage.Water-storage is to use at present in physics energy storage
At most, energy storage capacity is maximum, but water-storage is limited by geographical location, and the completion time of project is longer, other physics energy storage
Such as compressed-air energy storage, flywheel energy storage are all also not on a large scale.Electrochemical energy storage refer to by occur reversible chemical reaction come
Storage or release electricity, it with its high-energy conversion efficiency and power density, have extended cycle life, the construction period is short, maintenance cost
Common concern of the low advantage by people.
Stage now, electrochemical energy storage mainly include the high temperature sodium-sulphur battery, flow battery, lead-acid battery and lithium ion battery
Deng this several major class.The operating temperature of sodium-sulphur battery Na-S battery is 300 DEG C, and metallic sodium and elemental sulfur are in a molten state, if
Material under high temperature breakage is easy to cause fire in battery module, therefore safety problem is very big, fails large-scale application.Liquid stream electricity
Pond energy density is lower, volume is larger.Lead-acid battery accounts for always storage relative to Ni-Cd battery memory-less effect, at low cost at present
Most ratios in energy market, are widely used.But its disadvantage is also obvious, such as lead causes serious pollution to the environment, battery energy
Metric density is low, quality is heavy, volume is larger, and maintenance cost also will increase.Since energy-storage system needs to have low in cost, green ring
It protects, the features such as service life is long and security performance is high, in numerous electrochemical energy storage materials, lithium ion secondary battery and sodium ion two
Primary cell becomes technology important in energy storage technology.
Currently as electrochemical energy storage lithium ion battery with high-energy density, high circulation stability, long circulation life, body
The advantages that product is small light-weight and pollution-free, is widely applied in daily life.In view of sodium in the periodic table of elements with
Lithium belongs to alkali metal element, therefore has similar physicochemical properties.Sodium-ion battery and lithium ion battery have similar
Charge and discharge storage mechanism, it is often more important that sodium rich reserves and widely distributed in nature, there are also significant price advantages.
Other than sodium ion price is low, aluminium foil is can be used in the positive and negative anodes collector of sodium-ion battery, and negative electrode of lithium ion battery is only
Copper can be used, it is clear that much more expensive than aluminium of copper, therefore the cost of raw material is cheap and is easy to get, these advantages get over sodium-ion battery
To get over by worldwide extensive concern.
But current sodium-ion battery is also in conceptual phase, and there are no commercialized sodium-ion battery positive materials, now
Researcher is concentrated mainly on the research of sodium-ion battery the oxide anode material Na of layer structurexMO2(M represents 3d transition
It may include one or more, such as Ti, V, Cr, Fe, Mn, Co, Ni, Cu, Nb, Ru, Mo, Zn in metallic element).Battery
Basis is redox reaction, and the essence of reaction is that chemical valence changes, i.e., electronics has transfer and offset.The half-reaction of betatopic
It is oxidation reaction, the chemical valence of positive electrode increases；The half-reaction for obtaining electronics is reduction reaction, and chemical valence drops in positive electrode
It is low.And the transition that redox reaction can occur is all had in sodium-ion battery layered oxide positive electrode described above
Metal material, and the variable valency transition metal of material original state is in lower valence state.
Summary of the invention
The embodiment of the invention provides a kind of sodium magnesium manganese base layered oxide materials to appraise at the current rate with anion, preparation method
And purposes.Layered oxide material preparation is simple, and contained elements of Na, magnesium and manganese is all the element of non-toxic and safe, In
Abundance in the earth's crust is high, therefore manufacturing cost is cheap.Using the sodium ion secondary battery of layered oxide material of the invention, material
Material preparation is simple, and finds in half-cell test, the material not only specific discharge capacity with higher and specific energy, specific volume
Amount is 1.5 to 2 times of common sodium-ion battery positive material, and cycle life is preferable, has very big practical value, 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.
In a first aspect, the invention discloses a kind of sodium magnesium manganese base layered oxide material to appraise at the current rate with anion, it is described
The chemical general formula of material are as follows: Naa[MgbMnc]O2+β；
The a, b, c, β are respectively molar percentage shared by corresponding element；Relationship between wherein a, b, c, β meets b+
C=1, and a+b+4c=2 × (2+ β)；Wherein 0.5≤a≤0.85；0.25≤b≤0.425；0.575≤c≤0.75；-0.02
≤β≤0.02；
The space group of layered oxide material is P63/ mmc or P63/ mcm or R-3m, counter structure are P2 phase or P3
Phase；
The anion appraises at the current rate positive electrode active materials of the layered oxide material for sodium ion secondary battery, first week charging
When, the oxonium ion in lattice loses electronics, and the average valence of oxonium ion increases the valence state become between -2 and -1 from -2；It is first
When Zhou Fang electricity, the oxonium ion with higher valence state retrieves electronics；With going deep into for electric discharge, part manganese ion can obtain electricity
The average valence of son, manganese ion becomes trivalent from tetravalence；Since second week, oxonium ion and manganese ion are common in charge and discharge process
Participate in reversible receiving and losing electrons process.
Preferably, in first week charging, the oxonium ion in the lattice is by O2-It is changed intoWherein 0 < x < 4.
Second aspect, the embodiment of the invention provides a kind of systems of layered oxide material as described in above-mentioned first aspect
Preparation Method, the method are solid phase method, comprising:
By magnesia/carbonic acid of the sodium carbonate of stoichiometry 100wt%~108wt% of required sodium and required stoichiometry
Magnesium, manganese dioxide are mixed into presoma in proportion；
The presoma is uniformly mixed to get by precursor powder using the method for ball milling；
The precursor powder is placed in Muffle furnace, it is small that 2~24 are heat-treated in 600 DEG C~1000 DEG C of air atmosphere
When；
Precursor powder after heat treatment is ground, layered oxide material is obtained.
The third aspect, the embodiment of the invention provides a kind of systems of layered oxide material as described in above-mentioned first aspect
Preparation Method, the method are spray drying process, comprising:
By magnesia/carbonic acid of the sodium carbonate of stoichiometry 100wt%~108wt% of required sodium and required stoichiometry
Magnesium, manganese oxide are mixed into presoma in proportion；
It stirs evenly to form slurry after the presoma is added ethyl alcohol or water；
Precursor powder is obtained after being spray-dried to the slurry；
The precursor powder is placed in Muffle furnace, it is small that 2~24 are heat-treated in 600 DEG C~1000 DEG C of air atmosphere
When；
Precursor powder after heat treatment is ground, layered oxide material is obtained.
Fourth aspect, the embodiment of the invention provides a kind of systems of layered oxide material as described in above-mentioned first aspect
Preparation Method, the method are spray drying process, comprising:
Use the sodium nitrate, magnesium nitrate, manganese nitrate of stoichiometric ratio for presoma；
It stirs evenly to form slurry after the presoma is added ethyl alcohol or water；
Precursor powder is obtained after being spray-dried to the slurry；
The precursor powder is placed in Muffle furnace, it is small that 2~24 are heat-treated in 600 DEG C~1000 DEG C of air atmosphere
When；
Precursor powder after heat treatment is ground, layered oxide material is obtained.
5th aspect, the embodiment of the invention provides a kind of systems of layered oxide material as described in above-mentioned first aspect
Preparation Method, the method are sol-gel method, comprising:
By the sodium acetate of stoichiometry 100wt%~108wt% of required sodium or sodium nitrate or sodium carbonate or sodium sulphate, contain
There are magnesium, the nitrate of manganese or sulfate to be stoichiometrically dissolved in water or be dissolved in ethyl alcohol and is mixed into precursor solution；
It is stirred at 50 DEG C~100 DEG C, and appropriate chelating agent is added, be evaporated to form aqueous precursor gel；
The aqueous precursor gel is placed in crucible, under 200 DEG C~500 DEG C of air atmosphere, 2 hours of pre-burning；
It is heat-treated 2~24 hours at 600 DEG C~1000 DEG C again；
Precursor powder after heat treatment is ground, layered oxide material is obtained.
6th aspect, the embodiment of the invention provides a kind of systems of layered oxide material as described in above-mentioned first aspect
Preparation Method, the method are coprecipitation, comprising:
By the molten containing magnesium, the nitrate of manganese or sulfate or carbonate or hydroxide difference of required stoichiometric ratio
In the deionized water of certain volume, and it is respectively formed solution；
The solution is slowly added dropwise in a certain concentration and the ammonia spirit of pH value with peristaltic pump, generates sediment；
Obtained sediment is cleaned up with deionized water, is uniformly mixed with sodium carbonate according to stoichiometric ratio after drying
Obtained predecessor；
The predecessor is placed in crucible, under 600 DEG C~1000 DEG C of air atmosphere, is heat-treated 2~24 hours,
Obtain precursor powder；
Precursor powder after heat treatment is ground, layered oxide material is obtained.
7th aspect, the embodiment of the invention provides a kind of anode pole piece of sodium ion secondary battery, the anode pole piece
Include:
Collector, coated on the conductive additive and binder on the collector and as described in above-mentioned first aspect
Layered oxide material.
Eighth aspect, the embodiment of the invention provides a kind of sodium ions including anode pole piece described in above-mentioned 7th aspect
Secondary cell.
Preferably, the sodium ion secondary battery is for solar power generation, wind-power electricity generation, smart grid peak regulation, distribution electricity
It stands, the extensive energy storage device of backup power supply or communication base station.
Layered oxide material preparation provided in an embodiment of the present invention is simple, and contained elements of Na, magnesium and manganese is all nothing
The element of malicious safety, the abundance in the earth's crust is high, therefore manufacturing cost is cheap.Using the sodium of layered oxide material of the invention
Ion secondary battery, the first week charging negative divalent of lattice oxonium ion is to the valence transition between -2 and -1, and electronics is completely by oxonium ion
Activation to realize material is provided；It is that the oxonium ion for the higher valence state that this part loses electronics obtains again first when first Zhou Fang electricity
Electronics becomes negative divalent again by high-valence state, and with going deep into for electric discharge, part manganese ion can obtain electronics and be converted to trivalent by tetravalence；
Since second week, oxonium ion and manganese ion can participate in reversible receiving and losing electrons process jointly in charge and discharge process, final to realize
Relatively high discharge capacity finally realizes relatively high discharge capacity.Due to Mg2+With stronger charge interaction, it is difficult to
Na is moved to from transition metal layer+Layer, therefore compared to Nax[Li,Mn]O2Li in system+Transition can gradually be deviate from circulation
Metal layer is simultaneously dissolved into the situation in electrolyte, and sodium magnesium Mn-based material of the present invention has better structural stability, to have
Superior cycle performance.The material circulation better performances, have a safety feature, and have very big practical value, can be used for the sun
It can 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.
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 the XRD diagram of multiple layered oxide materials of different element molar percentages provided in an embodiment of the present invention
Spectrum；
Fig. 2 is the preparation method flow chart that the solid phase method that the embodiment of the present invention 2 provides prepares layered oxide material；
Fig. 3 is the preparation method flow chart that the spray drying process that the embodiment of the present invention 3 provides prepares layered oxide material；
Fig. 4 is the preparation method process that the sol-gel method that the embodiment of the present invention 4 provides prepares layered oxide material
Figure；
Fig. 5 is the preparation method flow chart that the coprecipitation that the embodiment of the present invention 5 provides prepares layered oxide material；
Fig. 6 is a kind of sodium-ion battery that provides of the embodiment of the present invention 6 in 1.5-4.5V charging and discharging curve figure；
Fig. 7 is a kind of sodium-ion battery that provides of the embodiment of the present invention 7 in 1.5-4.5V charging and discharging curve figure；
Fig. 8 is a kind of sodium-ion battery that provides of the embodiment of the present invention 8 in 1.5-4.5V charging and discharging curve figure；
Fig. 9 is a kind of sodium-ion battery that provides of the embodiment of the present invention 9 in 1.5-4.5V charging and discharging curve figure.
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 invention provides a kind of sodium magnesium manganese base layered oxide materials to appraise at the current rate with anion, preparation method
And purposes.Layered oxide material preparation is simple, and contained elements of Na, magnesium and manganese is all the element of non-toxic and safe, In
Abundance in the earth's crust is high, therefore manufacturing cost is cheap.Using the sodium ion two of sodium magnesium manganese base layered oxide material of the invention
Primary cell, material preparation is simple, and finds in half-cell test, the material not only specific discharge capacity with higher and ratio
Energy, specific capacity is 1.5 to 2 times of common sodium-ion battery positive material, and cycle life is preferable, has very big practical valence
Value can be used for the big rule of solar power generation, wind-power electricity generation, smart grid peak regulation, distribution power station, backup power supply or communication base station
Mould energy storage device.
The sodium magnesium manganese base layered oxide material provided by the invention to appraise at the current rate with anion, chemical general formula are as follows: Naa
[MgbMnc]O2+β；
A, b, c, β are respectively molar percentage shared by corresponding element；Relationship between wherein a, b, c, β meets b+c=
1, and a+b+4c=2 × (2+ β)；Wherein 0.5≤a≤0.85；0.25≤b≤0.425；0.575≤c≤0.75；-0.02≤β
≤0.02；
The space group of sodium magnesium manganese base layered oxide material of the present invention is P63/ mmc or P63/ mcm or R-3m, counter structure
For P2 phase or P3 phase.
The positive-active material of sodium ion secondary battery is used for the sodium magnesium manganese base layered oxide material that anion appraises at the current rate
Material.In first week charging (abjection of corresponding sodium ion), the oxonium ion in lattice loses electronics, by O2-It is changed into O2 x-, wherein 0
< x < 4, average valence increase the valence state become between -2 and -1 from -2；(the embedding of sodium ion is corresponded to when first Zhou Fang electricity
Enter), retrieve electronics with the oxonium ion of higher valence state, with deeply (sodium ion insertion increases) of electric discharge, part manganese from
Son can obtain electronics, and average valence can become trivalent from tetravalence；Since second week, in charge and discharge process oxonium ion and manganese from
Son can participate in reversible receiving and losing electrons process jointly.
Sodium magnesium manganese base layered oxide material of the invention, compared to Nax[Li,Mn]O2System layered oxide material, tool
There is superior cycle performance.This is because in Nax[Li,Mn]O2In system, Li+Transition metal can gradually be deviate from circulation
Layer is simultaneously dissolved into electrolyte, therefore cycle performance can gradually be deteriorated, and sodium magnesium manganese base layered oxide material of the invention by
In Mg2+With stronger charge interaction, it is difficult to move to Na from transition metal layer+Layer, therefore have better structure steady
It is qualitative, to have superior cycle performance.
Below to the preparation method for obtaining the material, it is illustrated.
Embodiment 2
Present embodiments provide a kind of preparation method of sodium magnesium manganese base layered oxide material, specially solid phase method, such as Fig. 2
It is shown, comprising:
Step 201, by the oxygen of the sodium carbonate of stoichiometry 100wt%~108wt% of required sodium and required stoichiometry
Change magnesium/magnesium carbonate, manganese dioxide is mixed into presoma in proportion；
Step 202, presoma is uniformly mixed to get by precursor powder using the method for ball milling；
Step 203, precursor powder is placed in Muffle furnace, in 600 DEG C~1000 DEG C of air atmosphere be heat-treated 2~
24 hours；
Step 204, the precursor powder after heat treatment is ground, obtains sodium magnesium manganese base layered oxide material.
The preparation method of sodium magnesium manganese base layered oxide material provided in this embodiment, can be used in preparing above-described embodiment
The base layered oxide material of sodium magnesium manganese described in 1.Method provided in this embodiment is simple and easy, low in cost, material therefor
It is safe and non-toxic, suitable for the application manufactured on a large scale.
Embodiment 3
A kind of preparation method of sodium magnesium manganese base layered oxide material, specially spray drying process are present embodiments provided,
As shown in Figure 3, comprising:
Step 301, by the oxygen of the sodium carbonate of stoichiometry 100wt%~108wt% of required sodium and required stoichiometry
Change magnesium/magnesium carbonate, manganese oxide is mixed into presoma in proportion；
Step 302, it will stir evenly to form slurry after presoma plus ethyl alcohol or water；
Step 303, precursor powder is obtained after being spray-dried to slurry；
Step 304, precursor powder is placed in Muffle furnace, in 600 DEG C~1000 DEG C of air atmosphere be heat-treated 2~
24 hours；
Step 305, the precursor powder after heat treatment is ground, obtains sodium magnesium manganese base layered oxide material.
The preparation method of sodium magnesium manganese base layered oxide material provided in this embodiment, can be used in preparing above-described embodiment
The base layered oxide material of sodium magnesium manganese described in 1.Method provided in this embodiment is simple and easy, low in cost, material therefor
It is safe and non-toxic, suitable for the application manufactured on a large scale.
Embodiment 4
A kind of preparation method of sodium magnesium manganese base layered oxide material, specially sol-gel method are present embodiments provided,
As shown in Figure 4, comprising:
Step 401, by the sodium acetate of stoichiometry 100wt%~108wt% of required sodium or sodium nitrate or sodium carbonate or
Sodium sulphate is stoichiometrically dissolved in water containing magnesium, the nitrate of manganese or sulfate or is dissolved in ethyl alcohol to be mixed into presoma molten
Liquid；
Step 402, it is stirred at 50 DEG C~100 DEG C, and appropriate chelating agent is added, be evaporated to form aqueous precursor gel；
Step 403, aqueous precursor gel is placed in crucible, it is pre-burning 2 small under 200 DEG C~500 DEG C of air atmosphere
When；
Step 404, it then at 600 DEG C~1000 DEG C is heat-treated 2~24 hours；
Step 405, the precursor powder after heat treatment is ground, obtains sodium magnesium manganese base layered oxide material.
The preparation method of sodium magnesium manganese base layered oxide material provided in this embodiment, can be used in preparing above-described embodiment
The base layered oxide material of sodium magnesium manganese described in 1.Method provided in this embodiment is simple and easy, low in cost, material therefor
It is safe and non-toxic, suitable for the application manufactured on a large scale.
Embodiment 5
A kind of preparation method of sodium magnesium manganese base layered oxide material, specially coprecipitation are present embodiments provided, such as
Shown in Fig. 5, comprising:
Step 501, required stoichiometric ratio is contained into magnesium, the nitrate of manganese or sulfate or carbonate or hydroxide
Object is dissolved in respectively in the deionized water of certain volume, and is respectively formed solution；
Step 502, solution is slowly added dropwise in a certain concentration and the ammonia spirit of pH value with peristaltic pump, generates precipitating
Object；
Step 503, obtained sediment is cleaned up with deionized water, with sodium carbonate according to stoichiometric ratio after drying
The predecessor being uniformly mixed to get；
Step 504, predecessor is placed in crucible, under 600 DEG C~1000 DEG C of air atmosphere, is heat-treated 2~24
Hour, obtain precursor powder；
Step 505, the precursor powder that heat treatment obtains is ground, obtains sodium magnesium manganese base layered oxide material.
The preparation method of sodium magnesium manganese base layered oxide material provided in this embodiment, can be used in preparing above-described embodiment
The base layered oxide material of sodium magnesium manganese described in 1.Method provided in this embodiment is simple and easy, low in cost, material therefor
It is safe and non-toxic, suitable for the application manufactured on a large scale.
The technical solution provided for a better understanding of the present invention, it is following to be illustrated respectively with multiple specific examples using the present invention
Several method provided by the above embodiment prepares the detailed process of sodium magnesium manganese base layered oxide material, and is applied to two
The method and battery behavior of primary cell.
Embodiment 6
Sodium magnesium manganese base layered oxide material is prepared using solid phase method described in previous embodiment 2 in the present embodiment, comprising:
By Na2CO3(analysis is pure), MgO (analysis is pure), MnO2(analysis is pure) is mixed by required stoichiometric ratio；It is ground in agate
Half an hour is ground in alms bowl, obtains presoma；Al will be transferred to after presoma tabletting2O3In crucible, in Muffle furnace at 600 DEG C
Reason 15 hours, obtains the layered oxide material Na of brown ceramic powder0.5Mg0.25Mn0.75O2, XRD spectrum is referring to Fig. 1, from XRD diagram
It is seen in spectrum, Na0.5Mg0.25Mn0.75O2Crystal structure be P3 phase layer structure oxide.
Sodium ion electricity is used for using the above-mentioned layered oxide material being prepared as the active material of cell positive material
The preparation in pond, specific steps are as follows: the Na that will be prepared0.5Mg0.25Mn0.75O2Powder and acetylene black, binder Kynoar
(PVDF) it is mixed according to the mass ratio of 80:10:10, suitable N-Methyl pyrrolidone (NMP) solution is added, in air drying
Grinding forms slurry in environment, and then slurry is evenly applied in current collector aluminum foil, and is cut into (8 after drying under infrared lamp
×8)mm2Pole piece.Pole piece under vacuum conditions, 110 DEG C drying 10 hours, it is spare to be transferred to glove box immediately.
It is carried out in the glove box for being assemblied in Ar atmosphere of simulated battery, using metallic sodium as to electrode, with NaClO4/ carbonic acid
Diethylester (EC:DEC) solution is assembled into CR2032 button cell as electrolyte.Using constant current charge-discharge mode, in C/10 electricity
Charge-discharge test is carried out under current density.It is 1.5V discharging by voltage, under conditions of voltage is 4.5V, test is tied for charging
Fruit sees Fig. 6.The charge and discharge cycles curve of first week He second week is shown in Fig. 6, it can be seen that its first all specific discharge capacity can
Up to 160.8mAh/g, second week coulombic efficiency is about 85.7%, stable circulation.
Embodiment 7
Sodium magnesium manganese base layered oxide material is prepared using solid phase method described in previous embodiment 2 in the present embodiment.
The specific preparation step of embodiment is with embodiment 6, but precursor compound Na used2CO3(analysis is pure), MgO (point
Analyse pure), MnO2The stoichiometry of (analysis is pure) is different from embodiment 6, and heat treatment condition is 600 DEG C, 15 hours, obtains black
The layered oxide material of powder is Na0.55Mg0.275Mn0.725O2, XRD spectrum is referring to Fig. 1.
Sodium ion electricity is used for using the above-mentioned layered oxide material being prepared as the active material of cell positive material
The preparation in pond, and carry out charge discharge test.Its preparation process and test method are the same as embodiment 6.Test voltage range is
1.5V~4.5V, test result are shown in Fig. 7.First week and second week charging and discharging curve are shown in Fig. 7.As can be seen that first put in week
Electric specific capacity is about 94.6% up to 164.0mAh/g, second week coulombic efficiency.
Embodiment 8
Layered oxide material is prepared using solid phase method described in previous embodiment 2 in the present embodiment.
The specific preparation step of embodiment is with embodiment 6, but precursor compound Na used2CO3(analysis is pure), MgO (point
Analyse pure), MnO2The stoichiometry of (analysis is pure) is different from embodiment 6, and heat treatment condition is 700 DEG C, 15 hours, obtains black
The layered oxide material of powder is Na0.6Mg0.3Mn0.7O2, XRD spectrum is referring to Fig. 1.
Sodium ion electricity is used for using the above-mentioned layered oxide material being prepared as the active material of cell positive material
The preparation in pond, and carry out charge discharge test.Its preparation process and test method are the same as embodiment 6.Test voltage range is
1.5V~4.4V, test result are shown in Fig. 8.First week and second week charging and discharging curve are shown in Fig. 8.As can be seen that first put in week
Electric specific capacity is about 97.9% up to 213.4mAh/g, second week coulombic efficiency.
Embodiment 9
Layered oxide material is prepared using solid phase method described in previous embodiment 2 in the present embodiment.
The specific preparation step of embodiment is with embodiment 6, but precursor compound Na used2CO3(analysis is pure), MgO (point
Analyse pure), MnO2The stoichiometry of (analysis is pure) is different from embodiment 6, and heat treatment condition is 900 DEG C, 15 hours, obtains black
The layered oxide material of powder is Na0.67Mg0.33Mn0.67O2, XRD spectrum is referring to Fig. 1.
Sodium ion electricity is used for using the above-mentioned layered oxide material being prepared as the active material of cell positive material
The preparation in pond, and carry out charge discharge test.Its preparation process and test method are the same as embodiment 6.Test voltage range is
1.5V~4.5V, test result are shown in Fig. 9.First week and second week charging and discharging curve are shown in Fig. 9.As can be seen that first put in week
Electric specific capacity is about 89.3% up to 137mAh/g, second week coulombic efficiency.
Sodium magnesium manganese base layered oxide material provided in an embodiment of the present invention preparation is simple, contained elements of Na, magnesium and
Manganese is all the element of non-toxic and safe, and the abundance in the earth's crust is high, therefore manufacturing cost is cheap.Using Na Mei manganese base of the invention
The sodium ion secondary battery of shape oxide material, material preparation is simple, and finds in half-cell test, which not only has
There are the specific discharge capacity and specific energy of superelevation, specific capacity is 1.5 to 2 times of common sodium-ion battery positive material, and recycles the longevity
Life preferably, have very big practical value, can be used for solar power generation, wind-power electricity generation, smart grid peak regulation, distribution power station, after
The extensive energy storage device of stand-by power source or communication base station.
Claims (10)
1. a kind of sodium magnesium manganese base layered oxide material to appraise at the current rate with anion, which is characterized in that layered oxide material
The chemical general formula of material are as follows: Naa[MgbMnc]O2+β；
The a, b, c, β are respectively molar percentage shared by corresponding element；Relationship between wherein a, b, c, β meets b+c=
1, and a+b+4c=2 × (2+ β)；Wherein 0.5≤a≤0.85；0.25≤b≤0.425；0.575≤c≤0.75；-0.02≤β
≤0.02；
The space group of layered oxide material is P63/ mmc or P63/ mcm or R-3m, counter structure are P2 phase or P3 phase；
The anion appraises at the current rate positive electrode active materials of the layered oxide material for sodium ion secondary battery, when first week charging,
Oxonium ion in lattice loses electronics, and the average valence of oxonium ion increases the valence state become between -2 and -1 from -2；First week
When electric discharge, the oxonium ion with higher valence state retrieves electronics；With going deep into for electric discharge, part manganese ion can obtain electronics,
The average valence of manganese ion becomes trivalent from tetravalence；Since second week, oxonium ion and manganese ion are joined jointly in charge and discharge process
With reversible receiving and losing electrons process.
2. layered oxide material according to claim 1, which is characterized in that in first week charging, in the lattice
Oxonium ion is by O2-It is changed intoWherein 0 < x < 4.
3. a kind of preparation method such as above-mentioned layered oxide material described in claim 1, which is characterized in that the method is
Solid phase method, comprising:
By the sodium carbonate of stoichiometry 100wt%~108wt% of required sodium and magnesia/magnesium carbonate of required stoichiometry,
Manganese dioxide is mixed into presoma in proportion；
The presoma is uniformly mixed to get by precursor powder using the method for ball milling；
The precursor powder is placed in Muffle furnace, is heat-treated 2~24 hours in 600 DEG C~1000 DEG C of air atmosphere；
Precursor powder after heat treatment is ground, layered oxide material is obtained.
4. a kind of preparation method such as above-mentioned layered oxide material described in claim 1, which is characterized in that the method is
Spray drying process, comprising:
By the sodium carbonate of stoichiometry 100wt%~108wt% of required sodium and magnesia/magnesium carbonate of required stoichiometry,
Manganese oxide is mixed into presoma in proportion；
It stirs evenly to form slurry after the presoma is added ethyl alcohol or water；
Precursor powder is obtained after being spray-dried to the slurry；
The precursor powder is placed in Muffle furnace, is heat-treated 2~24 hours in 600 DEG C~1000 DEG C of air atmosphere；
Precursor powder after heat treatment is ground, layered oxide material is obtained.
5. a kind of preparation method such as above-mentioned layered oxide material described in claim 1, which is characterized in that the method is
Spray drying process, comprising:
Use the sodium nitrate, magnesium nitrate, manganese nitrate of stoichiometric ratio for presoma；
It stirs evenly to form slurry after the presoma is added ethyl alcohol or water；
Precursor powder is obtained after being spray-dried to the slurry；
The precursor powder is placed in Muffle furnace, is heat-treated 2~24 hours in 600 DEG C~1000 DEG C of air atmosphere；
Precursor powder after heat treatment is ground, layered oxide material is obtained.
6. a kind of preparation method such as above-mentioned layered oxide material described in claim 1, which is characterized in that the method is
Sol-gel method, comprising:
By the sodium acetate of stoichiometry 100wt%~108wt% of required sodium or sodium nitrate or sodium carbonate or sodium sulphate, contain
Magnesium, the nitrate of manganese or sulfate, which are stoichiometrically dissolved in water or are dissolved in ethyl alcohol, is mixed into precursor solution；
It is stirred at 50 DEG C~100 DEG C, and appropriate chelating agent is added, be evaporated to form aqueous precursor gel；
The aqueous precursor gel is placed in crucible, under 200 DEG C~500 DEG C of air atmosphere, 2 hours of pre-burning；
It is heat-treated 2~24 hours at 600 DEG C~1000 DEG C again；
Precursor powder after heat treatment is ground, layered oxide material is obtained.
7. a kind of preparation method such as above-mentioned layered oxide material described in claim 1, which is characterized in that the method is
Coprecipitation, comprising:
Required stoichiometric ratio is dissolved in one containing magnesium, the nitrate of manganese or sulfate or carbonate or hydroxide respectively
Determine in the deionized water of volume, and is respectively formed solution；
The solution is slowly added dropwise in a certain concentration and the ammonia spirit of pH value with peristaltic pump, generates sediment；
Obtained sediment is cleaned up with deionized water, is uniformly mixed to get with sodium carbonate according to stoichiometric ratio after drying
Predecessor；
The predecessor is placed in crucible, under 600 DEG C~1000 DEG C of air atmosphere, 2~24 hours is heat-treated, obtains
Precursor powder；
Precursor powder after heat treatment is ground, layered oxide material is obtained.
8. a kind of anode pole piece of sodium ion secondary battery, which is characterized in that the anode pole piece includes:
Collector, coated on the conductive additive and binder on the collector and such as above-mentioned layer described in claim 1
Shape oxide material.
9. a kind of sodium ion secondary battery including anode pole piece described in the claims 8.
10. a kind of such as above-mentioned sodium ion secondary battery as claimed in claim 9, which is characterized in that the sodium ion secondary battery
For solar power generation, wind-power electricity generation, smart grid peak regulation, the extensive energy storage for being distributed power station, backup power supply or communication base station
Equipment.
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