CN109560258A - A kind of anion appraises at the current rate layered oxide material, preparation method and purposes - Google Patents

A kind of anion appraises at the current rate layered oxide material, preparation method and purposes Download PDF

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CN109560258A
CN109560258A CN201710879825.9A CN201710879825A CN109560258A CN 109560258 A CN109560258 A CN 109560258A CN 201710879825 A CN201710879825 A CN 201710879825A CN 109560258 A CN109560258 A CN 109560258A
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oxide material
layered oxide
sodium
precursor powder
preparation
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胡勇胜
容晓晖
陈立泉
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Institute of Physics of CAS
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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
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • 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
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • 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
    • H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
    • 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
    • H01M4/502—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese for non-aqueous cells
    • 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
    • H01M4/523—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron for non-aqueous cells
    • 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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  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
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Abstract

It appraises at the current rate layered oxide material, preparation method and purposes the invention discloses a kind of anion, the chemical general formula of material are as follows: Naa[LibMncMd]O2+β；M is that substituted element is doped to transition metal position；A, b, c, d, β are respectively molar percentage shared by corresponding element；Relationship between a, b, c, d, β meets b+c+d=1, and a+b+4c+md=2 (2+ β)；0.6≤a≤1；0<b≤0.4；0.5≤c≤0.8；0≤d≤0.3；-0.02≤β≤0.02；M is the valent state of M；The space group of material is P63/ mmc or R-3m, counter structure is P2 phase or P3 phase, and anion appraises at the current rate positive electrode active materials of the layered oxide material for sodium ion secondary battery, in first week charging, lattice oxonium ion is changed by negative divalent to higher price, the activation that electronics is provided completely by oxonium ion to realize material；When first Zhou Fang electricity, be first this part lose the oxonium ion of electronics again electronics becomes negative divalent again by high-valence state, rear manganese metal is converted to trivalent by tetravalence, and the charge and discharge process after second week has appraising at the current rate for oxonium ion and appraising at the current rate for manganese simultaneously.

Description

A kind of anion appraises at the current rate layered oxide material, preparation method and purposes
Technical field
It appraises at the current rate layered oxide material, preparation method the present invention relates to field of material technology more particularly to a kind of anion, And it is applied to the purposes of pole piece, secondary cell.
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 oxide anode material NaxMO2 of layer structure for the research of sodium-ion battery, and (M represents 3d mistake It crosses in metallic element, may include one or more, such as Ti, V, Cr, Fe, Mn, Co, Ni, Cu, Nb, Ru, Mo, Zn).Battery Basis be redox reaction, the essence of reaction is that chemical valence changes, i.e., electronics has transfer and offset.The half of betatopic is anti- It should be 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
It appraises at the current rate layered oxide material, preparation method, pole piece, secondary cell the embodiment of the invention provides a kind of anion And purposes.Layered oxide material preparation is simple, and contained elements of Na, lithium and manganese is all the element of non-toxic and safe, 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, which not only has the specific discharge capacity and specific energy of superelevation, specific volume Amount is two to three 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, appraise at the current rate layered oxide material the embodiment of the invention provides a kind of anion, chemical general formula are as follows: Naa[LibMncMd]O2+β；
Wherein, M is that substituted element, specially Ni are doped to transition metal position2+,Cu2+,Mg2+,Mn2+,Zn2+,Mn3 +,Al3+,Fe3+,B3+,Zr4+, Ti4+,Sn4+,Si4+One of or it is a variety of；
The a, b, c, d, β are respectively molar percentage shared by corresponding element；Relationship between wherein a, b, c, d, β is full Sufficient b+c+d=1, and a+b+4c+md=2 (2+ β)；Wherein 0.6≤a≤1；0<b≤0.4；0.5≤c≤0.8；0≤d≤0.3；- 0.02≤β≤0.02；M is the valent state of the M；
The space group of layered oxide material is P63/mmc or R-3m, and counter structure is P2 phase or P3 phase；
The anion appraise at the current rate layered oxide material for sodium ion secondary battery positive electrode active materials, filled in first week When electric, lattice oxonium ion is changed by negative divalent to higher price, the activation that electronics is provided completely by oxonium ion to realize material；It is first When Zhou Fang electricity, be first lose the oxonium ion of electronics again electronics becomes negative divalent again by high-valence state, manganese metal is by tetravalence later It is converted to trivalent, the charge and discharge process after second week has appraising at the current rate for oxonium ion and appraising at the current rate for manganese simultaneously.
Preferably, in first week charging, the lattice oxonium ion 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 lithium carbonate/hydrogen-oxygen of the sodium carbonate of stoichiometry 100wt%~108wt% of required sodium and required stoichiometry The oxide for changing lithium, manganese dioxide and M is mixed into presoma in proportion；The M is specially Ni2+,Cu2+,Mg2+,Mn2+,Zn2+, Mn3+,Al3+,Fe3+,B3+,Zr4+, Ti4+,Sn4+,Si4+One of or it is a variety of；
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 the sodium carbonate of stoichiometry 100wt%~108wt% of required sodium and the copper oxide of required stoichiometry, oxidation The oxide of iron, manganese oxide and M is mixed into presoma in proportion；The M is specially Ni2+,Cu2+,Mg2+,Mn2+,Zn2+,Mn3+, Al3+,Fe3+,B3+,Zr4+, Ti4+,Sn4+,Si4+One of or it is a variety of；
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 650 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 nitrate of the sodium nitrate of stoichiometric ratio, lithium nitrate, manganese nitrate and M for presoma；The M is specially Ni2+,Cu2+,Mg2+,Mn2+,Zn2+,Mn3+,Al3+,Fe3+,B3+,Zr4+, Ti4+,Sn4+,Si4+One of or it is a variety of；
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 650 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 lithium, manganese, the nitrate of doped chemical M or sulfate to be stoichiometrically dissolved in water or be dissolved in ethyl alcohol to be mixed into presoma molten Liquid；The M is specially Ni2+,Cu2+,Mg2+,Zn2+,Co2+,Ca2+,Ba2+,Sr2+,Al3+,Fe3+,B3+,Cr3+,Co3+,V3+,Zr4+, Ti4+,Sn4+,V4+,Mo4+,Mo5+, Ru4+, Nb5+,Si4+,Sb5+,Nb5+,Mo6+,Te6+One of or it is a variety of；
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:
The nitrate containing manganese and M or sulfate or carbonate or the hydroxide difference of required stoichiometric ratio is molten In the deionized water of certain volume, and it is respectively formed solution；The M is specially Ni2+,Cu2+,Mg2+,Mn2+,Zn2+,Mn3+, Al3+,Fe3+,B3+,Zr4+, Ti4+,Sn4+,Si4+One of or it is a variety of；
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, with sodium carbonate, lithium carbonate/lithium hydroxide according to change after drying Learn the predecessor that metering ratio is uniformly mixed to get；
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.
9th aspect, the embodiment of the invention provides a kind of use of sodium ion secondary battery as described in above-mentioned eighth aspect 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.
Layered oxide material preparation provided in an embodiment of the present invention is simple, and contained elements of Na, lithium 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 change to higher price, and electronics is provided completely by oxonium ion with reality The activation of existing material；When first Zhou Fang electricity, be first this part lose the oxonium ion of electronics again electronics become again by high-valence state it is negative Divalent, rear manganese metal are converted to trivalent by tetravalence, the charge and discharge process after second week simultaneously have oxonium ion appraise at the current rate and manganese Presence of appraising at the current rate, finally realize relatively high discharge capacity, cycle performance is preferable, have a safety feature, have very big practical value, It can be used for the extensive of solar power generation, wind-power electricity generation, smart grid peak regulation, distribution power station, backup power supply or communication base station Energy storage device.
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 the multiple layered oxide materials for the different element molar percentages that the embodiment of the present invention 1 provides 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；
Figure 10 is a kind of sodium-ion battery that provides of the embodiment of the present invention 9 in 2.0-4.5V charging and discharging curve figure；
Figure 11 is a kind of sodium-ion battery that provides of the embodiment of the present invention 10 in 1.5-4.5V charging and discharging curve figure；
Figure 12 is a kind of sodium-ion battery that provides of the embodiment of the present invention 11 in 1.5-4.5V charging and discharging curve figure；
Figure 13 is a kind of sodium-ion battery that provides of the embodiment of the present invention 12 in 1.5-4.5V charging and discharging curve figure；
Figure 14 is a kind of sodium-ion battery that provides of the embodiment of the present invention 13 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 present invention 1 provides a kind of anion and appraises at the current rate layered oxide material, which is characterized in that layered oxygen The chemical general formula of compound material are as follows: Naa[LibMncMd]O2+β；
Wherein, M is that substituted element, specially Ni are doped to transition metal position2+,Cu2+,Mg2+,Mn2+,Zn2+,Mn3 +,Al3+,Fe3+,B3+,Zr4+, Ti4+,Sn4+,Si4+One of or it is a variety of；
The a, b, c, d, β are respectively molar percentage shared by corresponding element；Relationship between wherein a, b, c, d, β is full Sufficient b+c+d=1, and a+b+4c+md=2 (2+ β)；Wherein 0.6≤a≤1；0<b≤0.4；0.5≤c≤0.8；0≤d≤0.3；- 0.02≤β≤0.02；M is the valent state of the M；
The space group of layered oxide material is P63/mmc or R-3m, and counter structure is P2 phase or P3 phase.
It has been presented in Fig. 1 the X-ray diffraction (X-ray of multiple layered oxide materials of different element molar percentages Diffraction, XRD) map, the Na provided in this embodiment it can be seen from XRD spectruma[LibMncMd]O2+βCrystal knot Structure is the oxide of the layer structure of P2 phase.
Layered oxide material of the invention is applied to sodium ion secondary battery, the first week charging negative divalent of lattice oxonium ion Change to higher price, the activation that electronics is provided completely by oxonium ion to realize material, wherein lattice oxonium ion is by O2-It is changed intoWherein 0 < x < 4；When first Zhou Fang electricity, be first this part lose the oxonium ion of electronics again electronics is become again by high-valence state Negative divalent, rear manganese metal are converted to trivalent by tetravalence, the charge and discharge process after second week simultaneously have oxonium ion appraise at the current rate and The presence of appraising at the current rate of manganese, finally realize relatively high discharge capacity and preferable cycle performance compared with.
Anion provided in an embodiment of the present invention appraises at the current rate layered oxide material preparation simply, contained elements of Na, lithium It is all the element of non-toxic and safe with manganese, the abundance in the earth's crust is high, therefore manufacturing cost is cheap.It is aoxidized using stratiform of the invention The sodium ion secondary battery of object material, material preparation is simple, and finds in half-cell test, which not only has superelevation Specific discharge capacity and specific energy, specific capacity is two to three times of common sodium-ion battery positive material, and cycle life is preferable, With very big practical value.
Below to the preparation method for obtaining the material, it is illustrated.
Embodiment 2
A kind of preparation method of layered oxide material, specially solid phase method are present embodiments provided, as shown in Fig. 2, packet It includes:
Step 201, by the carbon of the sodium carbonate of stoichiometry 100wt%~108wt% of required sodium and required stoichiometry The oxide of sour lithium/lithium hydroxide, manganese dioxide and M is mixed into presoma in proportion；
Specifically, the M is specially Ni2+,Cu2+,Mg2+,Mn2+,Zn2+,Mn3+,Al3+,Fe3+,B3+,Zr4+, Ti4+,Sn4+, Si4+One of or it is a variety of.
Step 202, the presoma is uniformly mixed to get by precursor powder using the method for ball milling；
Step 203, the precursor powder is placed in Muffle furnace, in 700 DEG C~1000 DEG C of air atmosphere at heat Reason 2~24 hours；
Step 204, the precursor powder after heat treatment is ground, obtains layered oxide material.
The preparation method of layered oxide material provided in this embodiment can be used in preparing described in above-described embodiment 1 Layered oxide material.Method provided in this embodiment is simple and easy, low in cost, material therefor is safe and non-toxic, is suitable for The application manufactured on a large scale.
Embodiment 3
A kind of preparation method of layered oxide material, specially spray drying process are present embodiments provided, such as Fig. 3 institute Show, comprising:
Step 301, 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 lithium, manganese, the nitrate of doped chemical M or sulfate or is dissolved in ethyl alcohol mixing At precursor solution；
Specifically, the M can be Ni2+,Cu2+,Mg2+,Mn2+,Zn2+,Mn3+,Al3+,Fe3+,B3+,Zr4+, Ti4+,Sn4+, Si4+One of or it is a variety of.
Step 302, it stirs evenly to form slurry after the presoma being added ethyl alcohol or water；
Step 303, precursor powder is obtained after being spray-dried to the slurry；
Step 304, the precursor powder is placed in Muffle furnace, in 650 DEG C~1000 DEG C of air atmosphere at heat Reason 2~24 hours；
Step 305, the precursor powder after heat treatment is ground, obtains layered oxide material.
The preparation method of layered oxide material provided in this embodiment can be used in preparing described in above-described embodiment 1 Layered oxide material.Method provided in this embodiment is simple and easy, low in cost, material therefor is safe and non-toxic, is suitable for The application manufactured on a large scale.
Embodiment 4
A kind of preparation method of layered oxide material, specially sol-gel method are present embodiments provided, such as Fig. 4 institute Show, 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 lithium, manganese, the nitrate of doped chemical M or sulfate or is dissolved in ethyl alcohol mixing At precursor solution；
Wherein, the M is specially Ni2+,Cu2+,Mg2+,Zn2+,Co2+,Ca2+,Ba2+,Sr2+,Al3+,Fe3+,B3+,Cr3+, Co3+,V3+,Zr4+, Ti4+,Sn4+,V4+,Mo4+,Mo5+, Ru4+, Nb5+,Si4+,Sb5+,Nb5+,Mo6+,Te6+One of or it is a variety of.
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, the aqueous precursor gel is placed in crucible, under 200 DEG C~500 DEG C of air atmosphere, pre-burning 2 Hour；
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 layered oxide material.
The preparation method of layered oxide material provided in this embodiment can be used in preparing described in above-described embodiment 1 Layered oxide material.Method provided in this embodiment is simple and easy, low in cost, material therefor is safe and non-toxic, is suitable for The application manufactured on a large scale.
Embodiment 5
A kind of preparation method of layered oxide material, specially coprecipitation are present embodiments provided, as shown in figure 5, Include:
Step 501, by the nitrate containing manganese and M or sulfate or carbonate or hydroxide of required stoichiometric ratio Object is dissolved in respectively in the deionized water of certain volume, and is respectively formed solution；
Wherein, the M is specially Ni2+,Cu2+,Mg2+,Mn2+,Zn2+,Mn3+,Al3+,Fe3+,B3+,Zr4+, Ti4+,Sn4+, Si4+One of or it is a variety of.
Step 502, the solution is slowly added dropwise in a certain concentration and the ammonia spirit of pH value with peristaltic pump, is generated Sediment；
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, the predecessor is placed in crucible, under 600 DEG C~1000 DEG C of air atmosphere, heat treatment 2~ 24 hours, obtain precursor powder；
Step 505, the precursor powder after heat treatment is ground, obtains layered oxide material.
The preparation method of layered oxide material provided in this embodiment can be used in preparing described in above-described embodiment 1 Layered oxide material.Method provided in this embodiment is simple and easy, low in cost, material therefor is safe and non-toxic, is 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 layered oxide material, and is applied to secondary cell Method and battery behavior.
Embodiment 6
Layered oxide material is prepared using solid phase method described in previous embodiment 2 in the present embodiment, comprising:
By Na2CO3(analysis is pure), LiOHH2O (analysis is pure), MgO (analysis is pure), MnO2(analysis is pure) presses required chemistry Metering is than mixing；Half an hour is ground in the agate mortar, obtains presoma；Al will be transferred to after presoma tabletting2O3In crucible, It is handled 12 hours at 700 DEG C in Muffle furnace, obtains the layered oxide material Na of brown ceramic powder0.6Li0.02Mg0.27Mn0.71O2, Its XRD spectrum is referring to Fig. 1, from XRD spectrum, Na0.6Li0.02Mg0.27Mn0.71O2Crystal structure be P2 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 prepared0.6Li0.02Mg0.27Mn0.71O2Powder and acetylene black, binder polyvinylidene fluoride Alkene (PVDF) is mixed according to the mass ratio of 80:10:10, suitable N-Methyl pyrrolidone (NMP) solution is added, in air drying Environment in grinding form slurry, then slurry is evenly applied in current collector aluminum foil, and it is dry under infrared lamp after, be cut into (8×8)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 4.4V, 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 90.4mAh/g, second week coulombic efficiency is about 98.2%, stable circulation.
Embodiment 7
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), LiOH H2O (analysis is pure), MnO2The stoichiometry of (analysis is pure) is different from embodiment 6, and heat treatment condition is 700 DEG C, 24 hours, obtains Layered oxide material to black powder is Na0.67Li0.22Mn0.78O2, 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 97.7% up to 232.2mAh/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), LiOH H2O (analysis is pure), MnO2The stoichiometry of (analysis is pure) is different from embodiment 6, and heat treatment condition is 700 DEG C, 24 hours, obtains Layered oxide material to black powder is Na0.69Li0.23Mn0.77O2, 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. 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 230.4mAh/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), LiOH H2O (analysis is pure), MnO2The stoichiometry of (analysis is pure) is different from embodiment 6, and heat treatment condition is 700 DEG C, 24 hours, obtains Layered oxide material to black powder is Na0.72Li0.24Mn0.76O2, 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 98.05% up to 268.6mAh/g, second week coulombic efficiency.
When test voltage range is 2.0V~4.5V, test result, which is shown in Figure 10 Figure 10, shows first week and second All charging and discharging curves.As can be seen that electric discharge cut-off is to 2.0V, first week specific discharge capacity is up to 200.2mAh/g, first week coulomb effect Rate is about 96.62%.
Embodiment 10
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), LiOH H2O (analysis is pure), MnO2The stoichiometry of (analysis is pure) is different from embodiment 6, and heat treatment condition is 700 DEG C, 24 hours, obtains Layered oxide material to black powder is Na0.75Li0.25Mn0.75O2, 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 Figure 11.First week and second week charging and discharging curve are shown in Figure 11.As can be seen that first week Specific discharge capacity is about 98.8% up to 237mAh/g, second week coulombic efficiency.
Embodiment 11
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), LiOH H2O (analysis is pure), MnO2The stoichiometry of (analysis is pure) is different from embodiment 6, and heat treatment condition is 700 DEG C, 24 hours, obtains Layered oxide material to black powder is Na0.84Li0.28Mn0.72O2, 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 Figure 12.First week and second week charging and discharging curve are shown in Figure 12.As can be seen that first week Specific discharge capacity is about 95.5% up to 222.8mAh/g, second week coulombic efficiency.
Embodiment 12
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), LiOH H2O (analysis is pure), MnO2The stoichiometry of (analysis is pure) is different from embodiment 6, and heat treatment condition is 700 DEG C, 24 hours, obtains Layered oxide material to black powder is Na1.0Li0.33Mn0.77O2, 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 Figure 13.First week and second week charging and discharging curve are shown in Figure 13.As can be seen that first week Specific discharge capacity is up to 169.5mAh/g, and first week coulombic efficiency is about 80.7%, and second week coulombic efficiency is about 91.9%.
Embodiment 13
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), LiOH H2O (analysis is pure), MgO (analysis is pure), MnO2The stoichiometry of (analysis is pure) is different from embodiment 6, heat treatment condition 700 DEG C, 24 hours, obtain black powder layered oxide material be Na0.70Li0.20Mg0.05Mn0.75O2, XRD spectrum is referring to figure 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 Figure 14.First week and second week charging and discharging curve are shown in Figure 14.As can be seen that first week Specific discharge capacity is about 99.2% up to 217.1mAh/g, second week coulombic efficiency.
Layered oxide material preparation provided in an embodiment of the present invention is simple, and contained elements of Na, lithium 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, material preparation is simple, and finds in half-cell test, which not only has the quality specific volume of superelevation Amount and specific energy, specific capacity is two to three times of common sodium-ion battery positive material, and cycle life is preferable, has very big reality With value, it can be used for solar power generation, wind-power electricity generation, smart grid peak regulation, distribution power station, backup power supply or communication base station Extensive energy storage device.

Claims (9)

  1. A kind of layered oxide material 1. anion appraises at the current rate, which is characterized in that the chemical general formula of layered oxide material are as follows: Naa[LibMncMd]O2+β；
    Wherein, M is that substituted element, specially Ni are doped to transition metal position2+,Cu2+,Mg2+,Mn2+,Zn2+,Mn3+,Al3 +,Fe3+,B3+,Zr4+, Ti4+,Sn4+,Si4+One of or it is a variety of；
    The a, b, c, d, β are respectively molar percentage shared by corresponding element；Relationship between wherein a, b, c, d, β meets b+ C+d=1, and a+b+4c+md=2 (2+ β)；Wherein 0.6≤a≤1；0<b≤0.4；0.5≤c≤0.8；0≤d≤0.3；-0.02 ≤β≤0.02；M is the valent state of the M；
    The space group of layered oxide material is P63/mmc or R-3m, and counter structure is 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, in first week charging When, lattice oxonium ion is changed by negative divalent to higher price, the activation that electronics is provided completely by oxonium ion to realize material；First week It is to lose the oxonium ion of electronics to retrieve electronics and become negative divalent again by high-valence state first, manganese metal is by tetravalence later when electric discharge It is converted to trivalent, the charge and discharge process after second week has appraising at the current rate for oxonium ion and appraising at the current rate for manganese simultaneously.
  2. 2. layered oxide material according to claim 1, which is characterized in that in first week charging, the Lattice Oxygen from Son is by O2-It is changed intoWherein 0 < x < 4.
  3. 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 lithium carbonate/hydroxide of the sodium carbonate of stoichiometry 100wt%~108wt% of required sodium and required stoichiometry The oxide of lithium, manganese dioxide and M is mixed into presoma in proportion；The M is specially Ni2+,Cu2+,Mg2+,Mn2+,Zn2+,Mn3 +,Al3+,Fe3+,B3+,Zr4+, Ti4+,Sn4+,Si4+One of or it is a variety of；
    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 700 DEG C~1000 DEG C of air atmosphere；
    Precursor powder after heat treatment is ground, layered oxide material is obtained.
  4. 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 the copper oxide of required stoichiometry, iron oxide, The oxide of manganese oxide and M are mixed into presoma in proportion；The M is specially Ni2+,Cu2+,Mg2+,Mn2+,Zn2+,Mn3+,Al3+, Fe3+,B3+,Zr4+, Ti4+,Sn4+,Si4+One of or it is a variety of；
    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 650 DEG C~1000 DEG C of air atmosphere；
    Precursor powder after heat treatment is ground, layered oxide material is obtained.
  5. 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 nitrate of the sodium nitrate of stoichiometric ratio, lithium nitrate, manganese nitrate and M for presoma；The M is specially Ni2+, Cu2+,Mg2+,Mn2+,Zn2+,Mn3+,Al3+,Fe3+,B3+,Zr4+, Ti4+,Sn4+,Si4+One of or it is a variety of；
    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 650 DEG C~1000 DEG C of air atmosphere；
    Precursor powder after heat treatment is ground, layered oxide material is obtained.
  6. 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 Lithium, manganese, the nitrate of doped chemical M or sulfate are stoichiometrically dissolved in water or are dissolved in ethyl alcohol to be mixed into presoma molten Liquid；The M is specially Ni2+,Cu2+,Mg2+,Zn2+,Co2+,Ca2+,Ba2+,Sr2+,Al3+,Fe3+,B3+,Cr3+,Co3+,V3+,Zr4+, Ti4+,Sn4+,V4+,Mo4+,Mo5+, Ru4+, Nb5+,Si4+,Sb5+,Nb5+,Mo6+,Te6+One of or it is a variety of；
    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. 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:
    The nitrate containing manganese and M or sulfate or carbonate or hydroxide of required stoichiometric ratio are dissolved in one respectively Determine in the deionized water of volume, and is respectively formed solution；The M is specially Ni2+,Cu2+,Mg2+,Mn2+,Zn2+,Mn3+,Al3+, Fe3+,B3+,Zr4+, Ti4+,Sn4+,Si4+One of or it is a variety of；
    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 counted with sodium carbonate, lithium carbonate/lithium hydroxide according to chemistry after drying The predecessor that amount ratio is uniformly mixed to get；
    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. 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. 9. a kind of sodium ion secondary battery including anode pole piece described in the claims 8, which is characterized in that the sodium from Sub- secondary cell is for solar power generation, wind-power electricity generation, smart grid peak regulation, distribution power station, backup power supply or communication base station Extensive energy storage device.
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WO2023082505A1 (en) * 2021-11-12 2023-05-19 中国科学院物理研究所 Oxide composite positive electrode material coated with borate in situ, preparation method, and use
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CN114122382B (en) * 2021-11-24 2024-04-02 西安交通大学 Layered positive electrode material of P3 type sodium ion battery, and preparation method and application thereof
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