CN110380024A - Sodium transition metal oxide of P3 structure and preparation method thereof and sodium-ion battery - Google Patents
Sodium transition metal oxide of P3 structure and preparation method thereof and sodium-ion battery Download PDFInfo
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- CN110380024A CN110380024A CN201910565507.4A CN201910565507A CN110380024A CN 110380024 A CN110380024 A CN 110380024A CN 201910565507 A CN201910565507 A CN 201910565507A CN 110380024 A CN110380024 A CN 110380024A
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- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
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- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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- 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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- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
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Abstract
The present invention relates to sodium-ion battery technical fields, specifically provide sodium transition metal oxide of a kind of P3 structure and preparation method thereof and sodium-ion battery.The sodium transition metal oxide of the P3 structure have it is following shown in general formula: NaxNiaMnbMcO2+d；Wherein, 0.9≤x≤1.1, a > 0, b > 0, c >=0, a+b+c=1, d >=0, M are selected from one or more of Cu, Mg, Fe, Zn, Ti, Co, Al.The sodium transition metal oxide of P3 structure of the present invention has stable P3 crystal phase structure, there is no sodium defects, be made after sodium-ion battery as sodium-ion battery positive electrode active materials be able to solve sodium ion deintercalation existing for conventional sodium-ion battery positive material and it is unstable to air the problems such as, be conducive to the commercial applications of sodium-ion battery.
Description
Technical field
The invention belongs to sodium-ion battery technical fields, and in particular to a kind of sodium transition metal oxide of P3 structure and its
Preparation method and sodium-ion battery.
Background technique
Sodium-ion battery is a kind of novel battery of most possible substitution lithium ion battery, wherein in sodium-ion battery more
Mature positive electrode is free from the layered cathode material of cobalt, and this material, which does not need addition cobalt, can have good stabilization
Property, transition metal oxide (the chemical general formula Na such as containing sodiumxTMO2, wherein TM represents the transition such as Mn, Ni, Fe, Ti, V gold
Belong to), specific capacity (100~190mAh/g) with higher, but since when voltage platform is lower for its specific capacity,
Corresponding sodium-ion battery also energy density is lower than the energy density of lithium ion battery.NaxTMO2The common crystal structure master of material
There are P2 and two kinds of O3, be specifically detailed in Fig. 1~4, wherein what P was represented is that sodium ion is located at prism center, and O is represented
Be that sodium ion is located at octahedra center, subsequent digital representation be transition metal layer in single structure cell the number of plies, P2
The XRD diagram of structure is as shown in Figure 2；The XRD of O3 structure is as shown in figure 4, it is embodied in peak height and peak area (104)
> (015).
Disclosing general formula in the prior art is NaxMn1-y-zLiyAzO2Sodium-ion battery positive material, wherein z < 0.2, y <
0.33 and 0.66 < x < 0.95, A Ti, Fe, Ni, Mg and Co etc.；Or general formula is NaxMn1-y-zMyM'zO2Sodium-ion battery
Positive electrode, wherein 0.6 < x < 1,0 < y < 0.4,0.05 < z < 0.2, M Ti, V, Cr, Zr, Al and Cu etc., M' Fe, Ni and Zn
Deng；Or general formula is Nax[MnaNibCoc]O2+ySodium-ion battery positive material, wherein 0.5≤x≤0.9, -0.1≤y≤
0.1, a+b+c=1,4a+2b+3c=4-x+2y and 0 < c≤0.5；Or general formula is Na0.7-xMn1-y-zNiyCozO2Sodium from
Sub- cell positive material, wherein 0 < x < 0.1,0.15 < y < 0.25,0.05 < z < 0.2 and 0.5 < 1-y-z < 0.7, these four materials
Belong to the positive electrode of P2 phase structure.Having the prior art to disclose general formula again is NaNi0.5Mn0.5-xTixO2Sodium-ion battery just
Pole material, this kind of positive electrode belong to the positive electrode of O3 phase structure.Reported P2 phase material is the sodium transition gold of sodium defect
Belong to oxide, in sodium-ion battery application shows as that enough sodium ions can not be provided, the sodium-ion battery being made from it
Energy density is lower.Although reported O3 phase positive electrode can not be the sodium transition metal oxide of sodium defect, but its is right
It is unstable in air, and there is the sodium ion deintercalation ability of difference, also result in the difficulty of its practical application.
Therefore it is desirable to develop positive electrode of the transition metal oxide of new sodium as sodium-ion battery, is reported
The Na in road0.67TMO2The crystal form of (TM represents the transition metal such as Mn, Ni, Fe, Ti, V) positive electrode is not belonging to P2 phase, is also not belonging to
O3 phase, but P3 phase structure as shown in Figure 5, but it is still the positive electrode of sodium defect, faces the difficulty of practical application.
Summary of the invention
For existing for current sodium-ion battery positive material since sodium defect causes sodium-ion battery energy density low or
Person is unstable to air to lead to problems such as sodium ion deintercalation ability poor, and the present invention provides a kind of sodium transiting metal oxidation of P3 structure
Object and preparation method thereof.
Further, the present invention also provides the sodium-ion batteries of the sodium transition metal oxide comprising P3 structure of the present invention.
For achieving the above object, technical scheme is as follows:
A kind of sodium transition metal oxide of P3 structure has general formula as follows:
NaxNiaMnbMcO2+d；
Wherein, 0.9≤x≤1.1, a > 0, b > 0, c >=0, a+b+c=1, d >=0, M be selected from Cu, Mg, Fe, Zn, Ti, Co,
One or more of Al.
Correspondingly, a kind of preparation method of the sodium transition metal oxide of P3 structure, comprising the following steps:
It is soluble in water after nickel salt, manganese salt, M salt are mixed, corresponding hybrid transition metal saline solution is obtained, use is coprecipitated
Shallow lake method precipitates obtained hybrid transition metal saline solution, and control pH value is 7.5-8.5, obtains transition metal carbonate
Precipitate presoma；According to stoichiometric ratio, by compounds containing sodium and transition metal carbonate precipitating presoma carry out mixing,
Sintering processes obtain the sodium transition metal oxide of P3 structure.
Further, a kind of sodium-ion battery, including positive electrode active materials, the positive electrode active materials include upper described
The preparation method system of the sodium transition metal oxide of P3 structure or the sodium transition metal oxide comprising the upper P3 structure
The sodium transition metal oxide of standby obtained P3 structure.
Technical effect of the invention are as follows:
Compared with the existing technology, the sodium transition metal oxide of P3 structure provided by the invention belongs to the sodium mistake of new crystal phase
Cross metal oxide, crystal form is P3 type, there is excellent structural stability, and sodium ion defect is not present, as sodium from
Have in good sodium ion deintercalation ability and air when sub- cell positive material and stablize, is conducive to the hair for pushing sodium-ion battery
Exhibition application.
The preparation method of the sodium transition metal oxide of P3 structure of the present invention, by the way of being co-precipitated combination calcining
It obtains, has raw material cheap and easy to get, the features such as preparation process is simple, the sodium transition metal oxide crystal form of the P3 structure of acquisition is complete
It is whole, purity is high.
Sodium-ion battery of the invention, since the active material of its anode is provided by the invention stable with satisfactory texture
Property and the P3 structure without sodium ion defect sodium transition metal oxide, solve traditional P2 phase transition metal oxide sodium lack
The problem of falling into, while solving the problems, such as that O3 phase transition metal oxide structural instability and sodium ion deintercalation ability are poor.
Detailed description of the invention
It to describe the technical solutions in the embodiments of the present invention more clearly, below will be to needed in the embodiment
Attached drawing is briefly described, it should be apparent that, drawings in the following description are only some embodiments of the invention, for ability
For the those of ordinary skill of domain, without creative efforts, it can also be obtained according to these attached drawings other attached
Figure.
Fig. 1 is NaxTMO2The common P2 crystal structure schematic diagram of material；
Fig. 2 is common P2 crystal structure materials (with Na0.67Ni0.33Mn0.67O2) XRD schematic diagram；
Fig. 3 is NaxTMO2The common O3 crystal structure schematic diagram of material；
Fig. 4 is the XRD diagram of common O3 crystal structure；
Fig. 5 is the crystal structure schematic diagram of the transition metal oxide of the sodium of P3 structure；
Fig. 6 is the XRD diagram of the transition metal oxide of the sodium of P3 structure；
Fig. 7 is the XRD diagram of the sodium transition metal oxide for the P3 structure that the embodiment of the present invention 1 is prepared；
Fig. 8 is the SEM figure of the sodium transition metal oxide for the P3 structure that the embodiment of the present invention 1 is prepared；
Fig. 9 is the XRD diagram of the sodium transition metal oxide for the P3 structure that the embodiment of the present invention 2 is prepared；
Figure 10 is the SEM figure of the sodium transition metal oxide for the P3 structure that the embodiment of the present invention 2 is prepared；
Figure 11 is the XRD diagram of the sodium transition metal oxide for the P3 structure that the embodiment of the present invention 3 is prepared；
Figure 12 is the SEM figure of the sodium transition metal oxide for the P3 structure that the embodiment of the present invention 3 is prepared；
Figure 13 is the first charge-discharge curve and cycle performance curve for the sodium-ion battery that application examples 1 of the present invention assembling obtains
Figure；
Figure 14 is the cycle performance curve graph for the sodium-ion battery that application examples 2 of the present invention assembling obtains；
Figure 15 is the cycle performance curve graph for the sodium-ion battery that application examples 3 of the present invention assembling obtains；
Figure 16 is the charging and discharging curve figure for the sodium-ion battery that application examples 4 of the present invention assembling obtains；
Figure 17 is the charging and discharging curve figure for the sodium-ion battery that application examples 5 of the present invention assembling obtains；
Figure 18 is the cycle performance curve graph for the sodium-ion battery that application examples 6 of the present invention assembling obtains；
Figure 19 is the cycle performance curve graph for the sodium-ion battery that application examples 7 of the present invention assembling obtains.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to the accompanying drawings and embodiments, right
The present invention is further elaborated.It should be appreciated that described herein, specific examples are only used to explain the present invention, not
For limiting the present invention.
An aspect of of the present present invention provides a kind of sodium transition metal oxide of P3 structure.The sodium transition gold of the P3 structure
Belong to oxide have it is lower shown in general formula:
NaxNiaMnbMcO2+d；
Wherein, 0.9≤x≤1.1, a > 0, b > 0, c >=0, a+b+c=1, d >=0, M be selected from Cu, Mg, Fe, Zn, Ti, Co,
One or more of Al.
Technical solution of the present invention is further explained in detail below.
The sodium transition metal oxide crystal form of P3 structure of the present invention as shown in figure 5, its with P3 crystal form, XRD spectrum such as Fig. 6
Shown, (015) peak value and peak area are greater than the peak value and peak area of (104).It specifically can be NaxNiaMnbO2+d、
NaxNiaMnbCucO2+d、NaxNiaMnbMgcO2+d、NaxNiaMnbFecO2+d、NaxNiaMnbZncO2+d、NaxNiaMnbTicO2+d、
NaxNiaMnbCocO2+d、NaxNiaMnbAlcO2+dAt least one of.
More specifically, it can be Na0.9Ni0.5Mn0.5O2、NaNi0.5Mn0.5O2、Na1.1Ni0.5Mn0.5O2、
NaNi0.5Mn0.48Cu0.02O2、NaNi0.5Mn0.48Mg0.01O2At least one of.These types of transition metal oxide, which has, to be stablized
Crystalline structure, be not present sodium defect problem, when being assembled into sodium-ion battery as sodium-ion battery positive electrode active materials,
Show good sodium ion deintercalation ability.
The second aspect of the present invention as a result, provides the preparation method of the sodium transition metal oxide of above-mentioned P3 structure, packet
Include following steps:
Nickel salt, manganese salt, M salt is soluble in water, corresponding hybrid transition metal saline solution is obtained, using coprecipitation pair
Obtained hybrid transition metal saline solution carries out coprecipitation reaction, obtains transition metal carbonate precipitate presoma；
According to stoichiometric ratio, compounds containing sodium and transition metal carbonate precipitating presoma are subjected to mixing, burnt
Knot processing, obtains the sodium transition metal oxide of P3 structure.
Detailed explanation is done to the preparation method below.
Nickel salt involved in raw material can be at least one of nickel sulfate, nickel acetate, nickel nitrate；The manganese salt is selected from sulphur
At least one of sour manganese, manganese acetate, manganese nitrate；And M salt can be sulfuric acid M salt, acetic acid M salt, nitric acid M salt, M indicate Cu, Mg,
One or more of Fe, Zn, Ti, Co, Al.
Before carrying out coprecipitation reaction, it is necessary to corresponding aqueous solution is made in nickel salt, manganese salt, M salt, to improve co-precipitation
The reaction efficiency of reaction.
During carrying out co-precipitation acquisition transition metal carbonate precipitating presoma, according to molar ratio, the nickel salt,
The ingredient proportion that manganese salt, M salt carry out coprecipitation reaction is 0.5-1:1:0-0.1.
When carrying out coprecipitation reaction, it is necessary to precipitating reagent be added thereto.Precipitating reagent used in the present invention is sodium carbonate
With the mixed solution of ammonium hydroxide, precipitating reagent adjusts the pH value of reaction system between 7.5~8.5, salt can be made within the scope of the pH
Class occurs co-precipitation and generates transition metal carbonate precipitating presoma, and advantageously forms P3 crystal form, and if pH is greater than 8.5,
Such as pH >=10.0, then be conducive to generate is O3 crystal form.
It is described to contain sodium according to molar ratio when compounds containing sodium and transition metal carbonate precipitating presoma carry out mixing
Close the sodium in object: transition metal carbonate precipitating presoma=(0.9~1.1): 1.
Preferably, the compounds containing sodium is at least one of sodium carbonate, sodium acetate, sodium hydroxide, and these types contains sodium
Compound after the completion of reaction, does not introduce new impurity, is conducive to the purity for further increasing product.
When compounds containing sodium and transition metal carbonate precipitating presoma are carried out mixing treatment, mechanical lapping can be used
Mode, the two can also be made to solution, mix and slurry simultaneously is made by ultrasonic vibration processing, and pass through drying, ball milling etc.
The purpose of mode, mixing is so that compounds containing sodium is uniformly mixed with transition metal carbonate precipitating presoma, convenient for sintering into
Transition metal oxide with P3 structure.
The sintering condition is as follows: first Isothermal sinter (1~5) h in (450~550) DEG C, then is warming up to (700~900)
DEG C and Isothermal sinter (10~24) h.
The features such as preparation method raw material of the invention is cheap and easy to get, and preparation process is simple, yield is high, the sodium transition gold of acquisition
The features such as belonging to oxide is P3 crystal form material, has crystal form complete, with high purity.
The sodium transition metal oxide of P3 structure obtained due to the present invention due to be P3 crystal form material, have and stablize
Crystalline structure, and be not present sodium defect problem, when being used as sodium-ion battery positive electrode active materials, be not present P2, O3
The sodium transition metal oxide of crystal form there are the problem of.Therefore, the present invention also provides with the sodium oxo transition metal of above-mentioned P3 structure
Positive plate, the sodium-ion battery of compound.
Wherein, positive plate with the sodium transition metal oxide of P3 structure as a positive electrode active material, while also containing conduction
Agent and binder.The sodium transition metal oxide of P3 structure and conductive agent, binder and solvent are specifically mixed and made into anode
Slurry is coated on plus plate current-collecting body surface, positive plate is made through drying, roll-in, cut-parts.The sodium transition gold of P3 structure in positive plate
Belong to oxide, conductive agent, binder mass ratio be 8:1:1.When preparing anode sizing agent, solvent can be N- crassitude
Ketone (NMP).
Sodium-ion battery includes the sodium transition gold in above-mentioned positive plate or positive electrode active materials containing P3 structure of the present invention
Belong to oxide.
Sodium transiting metal oxidation in the positive electrode active materials of sodium-ion battery of the present invention, in addition to containing P3 structure of the present invention
Beyond the region of objective existence, can also at least one of the positive electrode containing P2 phase structure, O3 phase positive electrode.
Sodium-ion battery provided by the invention, the negative electrode active material used is hard carbon or contains titanyl compound.
Electrolyte is 1M NaPF6Electrolyte, the 1M NaPF of/(EC:DMC=1:1)6Electrolyte, the 1M NaClO of/PC4/
(EC:PC=1:1) any one of electrolyte, wherein EC:DMC=1:1 indicate ethylene carbonate and methyl ethyl carbonate according to
Volume ratio is the solvent that 1:1 is formed, and PC indicates that propene carbonate, EC:PC indicate ethylene carbonate and propene carbonate according to body
Product is than the solvent for 1:1 formation.
Sodium-ion battery provided by the invention, the diaphragm used are the MIcroporous polyolefin films such as polyethylene, polypropylene, such as
Celgard diaphragm.
More effectively to illustrate technical solution of the present invention, technology of the invention is illustrated below by multiple specific embodiments
Scheme.
Embodiment 1
A kind of preparation method of the sodium transition metal oxide of P3 structure, includes the following steps:
(a) nickel sulfate and manganese sulfate are the ratio mixed dissolution Yu Shuizhong of 1:1 with molar ratio by, are configured to 2mol/L sulphur
The hybrid transition metal salting liquid of sour nickel and manganese sulfate, using 2mol/L sodium carbonate and the mixed aqueous solution conduct of 0.2mol/L ammonium hydroxide
Precipitating reagent, control pH value is about 8.0, and co-precipitation prepares nickel manganese carbonate precursor.
(b) the nickel manganese carbonate precursor that obtains sodium carbonate and step (a) is mixed according to the ratio that molar ratio is 0.45:1
Conjunction is placed in resistance-type heating air atmosphere stove Isothermal sinter 5h at 500 DEG C, then heats to 800 DEG C and Isothermal sinter 20h,
Cooled to room temperature obtains sample 1.
XRD, ICP and SEM test are carried out to gained sample 1, specific test result is detailed in Fig. 7,8.Wherein, ICP test knot
Fruit shows Na:Ni:Mn=0.92:0.50:0.50, and (104) peak is far below (015) peak, (104) peak area in the XRD spectra of Fig. 7
Again smaller than (015) peak area, it was demonstrated that the material of acquisition is P3 structure, therefore gained sample 1 is P3 structure
Na0.9Ni0.5Mn0.5O2；From figure 8, it is seen that it is that have the particle of layer structure, and the size of layer structure particle is in Asia
Micron order.
Embodiment 2
A kind of preparation method of the sodium transition metal oxide of P3 structure, includes the following steps:
(a) nickel sulfate and manganese sulfate are the ratio mixed dissolution Yu Shuizhong of 1:1 with molar ratio by, are configured to 1.5mol/L
The hybrid transition metal salting liquid of nickel sulfate and manganese sulfate is mixed using 1.5mol/L sodium carbonate with 0.15mol/L ammonium hydroxide water-soluble
Liquid is as precipitating reagent, and controlling pH value is about 8.0, and co-precipitation prepares nickel manganese carbonate precursor.
(b) the nickel manganese carbonate precursor that obtains sodium carbonate and step (a) is mixed according to the ratio that molar ratio is 0.50:1
Conjunction is placed in resistance-type heating air atmosphere stove Isothermal sinter 3h at 500 DEG C, then heats to 750 DEG C and Isothermal sinter 15h,
Cooled to room temperature obtains sample 2.
XRD, ICP and SEM test are carried out to gained sample 2, specific test result is detailed in Fig. 9,10.Wherein, ICP test knot
Fruit shows Na:Ni:Mn=1.03:0.51:0.50, and (104) peak is far below (015) peak, (104) peak area in the XRD spectra of Fig. 9
Again smaller than (015) peak area, it was demonstrated that the material of acquisition is P3 structure, therefore gained sample 2 is the NaNi of P3 structure0.5Mn0.5O2；
From fig. 10 it can be seen that its particle with layer structure, and the size of layer structure particle is in submicron order.
Embodiment 3
A kind of preparation method of the sodium transition metal oxide of P3 structure, includes the following steps:
(a) nickel sulfate and manganese sulfate are the ratio mixed dissolution Yu Shuizhong of 1:1 with molar ratio by, are configured to 1.0mol/L
The hybrid transition metal salting liquid of nickel sulfate and manganese sulfate is mixed using 1.0mol/L sodium carbonate with 0.10mol/L ammonium hydroxide water-soluble
Liquid is as precipitating reagent, and controlling pH value is about 8.0, and co-precipitation prepares nickel manganese carbonate precursor.
(b) the nickel manganese carbonate precursor that obtains sodium carbonate and step (a) is mixed according to the ratio that molar ratio is 0.55:1
Conjunction is placed in resistance-type heating air atmosphere stove Isothermal sinter 2h at 500 DEG C, then heats to 700 DEG C and Isothermal sinter 10h,
Cooled to room temperature obtains sample 3.
XRD, ICP and SEM test are carried out to gained sample 3, specific test result is detailed in Figure 11,12.Wherein, ICP is tested
(104) peak is far below (015) peak, (104) peak in the XRD spectra of Na:Ni:Mn=1.09:0.49:0.50 as the result is shown, Figure 11
Area is again smaller than (015) peak area, it was demonstrated that the material of acquisition is P3 structure, therefore gained sample 3 is P3 structure
Na1.1Ni0.5Mn0.5O2；It can be recognized from fig. 12 that its particle with layer structure, and the size of layer structure particle is in sub-micro
Meter level.
Embodiment 4
A kind of preparation method of the sodium transition metal oxide of P3 structure, includes the following steps:
(a) by nickel sulfate, manganese sulfate and copper sulphate with molar ratio for 0.5:0.48:0.02 ratio mixed dissolution in water
In, be configured to the hybrid transition metal salting liquid of 1.0mol/L nickel sulfate and manganese sulfate, using 1.0mol/L sodium carbonate with
0.10mol/L ammonium hydroxide mixed aqueous solution is as precipitating reagent, and controlling pH value is about 8.0, and co-precipitation prepares nickel copper-manganese carbonic acid salt precursor
Body.
(b) ratio that the nickel copper-manganese carbonate precursor that obtains sodium carbonate and step (a) is 0.50:1 according to molar ratio
Mixing is placed in resistance-type heating air atmosphere stove Isothermal sinter 2h at 500 DEG C, then heats to 700 DEG C and Isothermal sinter
10h, cooled to room temperature obtain sample 4.
XRD and ICP test is carried out to gained sample 4.Wherein, ICP test result shows Na:Ni:Mn:Cu=1.02:
0.51:0.48:0.02, (104) peak is far below (015) peak in XRD spectra, and (104) peak area is again smaller than (015) peak area, card
Bright is P3 structure, therefore gained sample 4 is the NaNi of P3 structure0.5Mn0.5Cu0.02O2。
Embodiment 5
A kind of preparation method of the sodium transition metal oxide of P3 structure, includes the following steps:
(a) by nickel sulfate, manganese sulfate and magnesium sulfate with molar ratio for 0.5:0.49:0.01 ratio mixed dissolution in water
In, it is configured to the hybrid transition metal salting liquid of 1.0mol/L nickel sulfate, manganese sulfate and magnesium sulfate, using 1.0mol/L sodium carbonate
With 0.10mol/L ammonium hydroxide mixed aqueous solution as precipitating reagent, controlling pH value is about 8.0, before co-precipitation prepares nickel manganese magnesium carbonate
Drive body.
(b) ratio that the nickel manganese magnesium carbonate presoma that obtains sodium carbonate and step (a) is 0.50:1 according to molar ratio
Mixing is placed in resistance-type heating air atmosphere stove Isothermal sinter 2h at 500 DEG C, then heats to 700 DEG C and Isothermal sinter
10h, cooled to room temperature obtain sample 5.
XRD and ICP test is carried out to gained sample 5.Wherein, ICP test result shows Na:Ni:Mn:Mg=1.01:
0.50:0.49:0.01, (104) peak is far below (015) peak in XRD spectra, and (104) peak area is again smaller than (015) peak area, card
Bright is P3 structure, therefore gained sample 5 is the NaNi of P3 structure0.5Mn0.5Mg0.01O2。
Application examples 1
A kind of sodium-ion battery, preparation method includes the following steps:
(1) Na that obtains embodiment 10.9Ni0.5Mn0.5O2As positive electrode active materials, with conductive black, polyvinylidene fluoride
Alkene (PVdF) binder is dissolved in N-Methyl pyrrolidone (NMP) solvent after mixing according to the ratio that mass ratio is 8:1:1 to be made
Anode sizing agent, and be coated on aluminium foil and obtain positive plate through drying, cutting.
(2) positive plate that step (1) obtains and sodium metal, Celgard diaphragm are assembled into sodium-ion battery by, the sodium from
The electrolyte of sub- battery is 1M NaPF6It is dissolved in the electrolyte that the EC/DMC that volume ratio is 1:1 is formed, stands voltage stabilization for 24 hours
Afterwards, charge-discharge test is carried out to it, test result is as shown in figure 13.
Specifically, test mode are as follows: initial charge capacity is under 10mA/g current density in 1.5-4.5V voltage range
141mAh/g, specific discharge capacity 140mAh/g；It through 500 circulation volume conservation rates is 78% under 100mA/g current density.
Application examples 2
A kind of sodium-ion battery, preparation method includes the following steps:
(1) NaNi that obtains embodiment 20.5Mn0.5O2As positive electrode active materials, with conductive black, PVdF binder
Anode sizing agent is made according to being dissolved in N-Methyl pyrrolidone (NMP) solvent after the ratio mixing that mass ratio is 8:1:1, and is coated with
Positive plate is obtained through drying, cutting on aluminium foil.
(2) positive plate that step (1) obtains and sodium metal, Celgard diaphragm are assembled into sodium-ion battery by, the sodium from
The electrolyte of sub- battery is 1M NaPF6It is dissolved in the electrolyte that the EC/DMC that volume ratio is 1:1 is formed, stands voltage stabilization for 24 hours
Afterwards, charge-discharge test is carried out to it, test result is as shown in figure 14.
Specifically, test mode are as follows: the first discharge specific capacity under 100mA/g current density in 1.5-4.5V voltage range
For 93mAh/g, capacity retention ratio is 55% after 400 circulations.
Application examples 3
A kind of sodium-ion battery, preparation method includes the following steps:
(1) Na that obtains embodiment 31.1Ni0.5Mn0.5O2As positive electrode active materials, bonded with conductive black, PVdF
Agent is dissolved in N-Methyl pyrrolidone (NMP) solvent after mixing according to the ratio that mass ratio is 8:1:1 is made anode sizing agent, and applies
Cloth obtains positive plate through drying, cutting on aluminium foil.
(2) positive plate that step (1) obtains and sodium metal, Celgard diaphragm are assembled into sodium-ion battery by, the sodium from
The electrolyte of sub- battery is 1M NaPF6It is dissolved in the electrolyte that the EC/DMC that volume ratio is 1:1 is formed, stands voltage stabilization for 24 hours
Afterwards, charge-discharge test is carried out to it, test result is as shown in figure 15.
Specifically, test mode are as follows: the first discharge specific capacity under 100mA/g current density in 1.5-4.5V voltage range
For 73mAh/g, capacity retention ratio is 51% after 400 circulations.
Application examples 4
A kind of sodium-ion battery, preparation method includes the following steps:
(1) Na that obtains embodiment 10.9Ni0.5Mn0.5O2As positive electrode active materials, bonded with conductive black, PVdF
Agent is dissolved in N-Methyl pyrrolidone (NMP) solvent after mixing according to the ratio that mass ratio is 8:1:1 is made anode sizing agent, and applies
Cloth obtains positive plate through drying, cutting on aluminium foil.
(2) positive plate that step (1) obtains and sodium metal, Celgard diaphragm are assembled into sodium-ion battery by, the sodium from
The electrolyte of sub- battery is 1M NaPF6It is dissolved in the electrolyte that the EC/DMC that volume ratio is 1:1 is formed, stands voltage stabilization for 24 hours
Afterwards, charge-discharge test is carried out to it, test result is as shown in figure 16.
Specifically, test mode are as follows: the charge and discharge under 10mA/g current density in 1.5-4.0V voltage range, it can from Figure 16
To find out, the 5th, the 20th time, the 40th charging curve be almost overlapped, illustrate that charge stability is good；The 4th, the 10th time,
30th time, the 50th discharge curve be almost overlapped, illustrate that discharge stability is good.
Application examples 5
A kind of sodium-ion battery, preparation method includes the following steps:
(1) Na that obtains embodiment 10.9Ni0.5Mn0.5O2As positive electrode active materials, bonded with conductive black, PVdF
Agent is dissolved in N-Methyl pyrrolidone (NMP) solvent after mixing according to the ratio that mass ratio is 8:1:1 is made anode sizing agent, and applies
Cloth obtains positive plate through drying, cutting on aluminium foil.
(2) positive plate that step (1) obtains and sodium metal, Celgard diaphragm are assembled into sodium-ion battery by, the sodium from
The electrolyte of sub- battery is 1M NaPF6It is dissolved in the electrolyte that the EC/DMC that volume ratio is 1:1 is formed, stands voltage stabilization for 24 hours
Afterwards, charge-discharge test is carried out to it, test result is as shown in figure 17.
Specifically, test mode are as follows: the charge and discharge under 100mA/g current density in 2.0-4.0V voltage range, from Figure 14
As can be seen that the 5th, the 20th time, the 40th charging curve be almost overlapped, illustrate that charge stability is good；The 4th, the 10th
It is secondary, the 30th time, the 50th discharge curve be almost overlapped, illustrate that discharge stability is good.
Application examples 6
A kind of sodium-ion battery, preparation method includes the following steps:
(1) Na that obtains embodiment 10.9Ni0.5Mn0.5O2As positive electrode active materials, bonded with conductive black, PVdF
Agent is dissolved in N-Methyl pyrrolidone (NMP) solvent after mixing according to the ratio that mass ratio is 8:1:1 is made anode sizing agent, and applies
Cloth obtains positive plate through drying, cutting on aluminium foil.
(2) positive plate that step (1) obtains and sodium metal, Celgard diaphragm are assembled into sodium-ion battery by, the sodium from
The electrolyte of sub- battery is 1M NaPF6It is dissolved in the electrolyte of PC formation, after standing voltage stabilization for 24 hours, charge and discharge are carried out to it
Test, test result are as shown in figure 18.
Specifically, test mode are as follows: hold under 100mA/g current density through 400 circulations in 1.5-4.5V voltage range
Measuring conservation rate is 21%.
Application examples 7
A kind of sodium-ion battery, preparation method includes the following steps:
(1) Na that obtains embodiment 10.9Ni0.5Mn0.5O2As positive electrode active materials, bonded with conductive black, PVdF
Agent is dissolved in N-Methyl pyrrolidone (NMP) solvent after mixing according to the ratio that mass ratio is 8:1:1 is made anode sizing agent, and applies
Cloth obtains positive plate through drying, cutting on aluminium foil.
(2) positive plate that step (1) obtains and sodium metal, Celgard diaphragm are assembled into sodium-ion battery by, the sodium from
The electrolyte of sub- battery is 1M NaClO4It is dissolved in the electrolyte that the EC/PC that volume ratio is 1:1 is formed, stands voltage stabilization for 24 hours
Afterwards, charge-discharge test is carried out to it, test result is as shown in figure 19.
Specifically, test mode are as follows: hold under 100mA/g current density through 400 circulations in 1.5-4.5V voltage range
Measuring conservation rate is 19%.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Made any modifications, equivalent replacements, and improvements etc. within mind and principle should all include within protection scope of the present invention.
Claims (10)
1. a kind of sodium transition metal oxide of P3 structure, which is characterized in that the sodium transition metal oxide has following institute
The general formula shown:
NaxNiaMnbMcO2+d；
Wherein, 0.9≤x≤1.1, a > 0, b > 0, c >=0, a+b+c=1, d >=0, M are in Cu, Mg, Fe, Zn, Ti, Co, Al
One or more.
2. the sodium transition metal oxide of P3 structure as described in claim 1, which is characterized in that the sodium transiting metal oxidation
Object is Na0.9Ni0.5Mn0.5O2、NaNi0.5Mn0.5O2、Na1.1Ni0.5Mn0.5O2、NaNi0.5Mn0.48Cu0.02O2、
NaNi0.5Mn0.48Mg0.01O2At least one of.
3. the preparation method of the sodium transition metal oxide such as the described in any item P3 structures of claim 1~2, feature exist
In, comprising the following steps:
It is soluble in water after nickel salt, manganese salt, M salt are mixed, corresponding hybrid transition metal saline solution is obtained, using coprecipitation
Obtained hybrid transition metal saline solution is precipitated, control pH value is 7.5-8.5, obtains transition metal carbonate precipitate
Presoma；
According to stoichiometric ratio, at compounds containing sodium and transition metal carbonate precipitating presoma progress mixing, sintering
Reason, obtains the sodium transition metal oxide of P3 structure.
4. the preparation method of the sodium transition metal oxide of P3 structure as claimed in claim 3, which is characterized in that described coprecipitated
It forms sediment and needs to be added precipitating reagent in reacting, the precipitating reagent is the sodium carbonate of (1-2) mol/L and the ammonium hydroxide of (0.1-0.2) mol/L
Mixed solution.
5. the preparation method of the sodium transition metal oxide of P3 structure as claimed in claim 3, which is characterized in that according to mole
Than the ingredient proportion that the nickel salt, manganese salt, M salt carry out coprecipitation reaction is 0.5-1:1:0-0.1.
6. the preparation method of the sodium transition metal oxide of P3 structure as claimed in claim 3, which is characterized in that according to mole
Than sodium in the compounds containing sodium: transition metal carbonate precipitates presoma=(0.9~1.1): 1.
7. the preparation method of the sodium transition metal oxide of P3 structure as claimed in claim 3, which is characterized in that the sintering
Condition is first Isothermal sinter (1~5) h in (450~550) DEG C, then be warming up to (700~900) DEG C and Isothermal sinter (10~
24)h。
8. the preparation method of the sodium transition metal oxide of P3 structure as claimed in claim 3, which is characterized in that the nickel salt
Selected from least one of nickel sulfate, nickel acetate, nickel nitrate；The manganese salt in manganese sulfate, manganese acetate, manganese nitrate at least
It is a kind of；The compounds containing sodium is at least one of sodium hydroxide, sodium carbonate, sodium acetate.
9. a kind of sodium-ion battery, including positive electrode active materials, which is characterized in that the positive electrode active materials include claim
The sodium transition metal oxide of 1~2 described in any item P3 structures includes the described in any item P3 knots of claim 3~8
The sodium transition metal oxide for the P3 structure that the preparation method of the sodium transition metal oxide of structure is prepared.
10. sodium-ion battery as claimed in claim 9, which is characterized in that also contain P2 phase mistake in the positive electrode active materials
Cross at least one of metal oxide, O3 phase transition metal oxide.
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| CN111180688A (en) * | 2019-12-30 | 2020-05-19 | 中南大学 | Micron-scale hollow porous sodium-ion battery positive electrode material and preparation method thereof |
| CN111628164A (en) * | 2020-05-22 | 2020-09-04 | 兰州理工大学 | Sodium ion battery positive electrode material and preparation method thereof |
| CN112624209A (en) * | 2020-12-18 | 2021-04-09 | 辽宁科技大学 | Na-Ti-Mg co-doped ternary material and preparation method and application thereof |
| WO2021150168A1 (en) * | 2020-01-21 | 2021-07-29 | National University Of Singapore | Na excess p3-type layered oxides naxmyoz with x ≥ 0.66; 0.8 ≤ y ≤ 1.0 and z ≤ 2 as cathode materials for sodium ion batteries |
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