CN109830679A - A kind of positive electrode material precursor, and its preparation method and application - Google Patents
A kind of positive electrode material precursor, and its preparation method and application Download PDFInfo
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Abstract
The present invention relates to a kind of positive electrode material precursor, and its preparation method and application, the chemical formula of the positive electrode material precursor is FeaMnbNicMd(OH)x, wherein 0<a<1,0<b<1,0<c<1, a+b+c>=0.90,0.01<d≤0.1, a+b+c+d=1,2<x<3；The M includes the combination of any one in Al element, Cu element and Co element or at least two.The present invention improves the interlamellar spacing of positive electrode material precursor by the way of adulterating M element, and then improves the structural stability of positive electrode material precursor；Meanwhile positive electrode material precursor can be effectively reduced to the sensibility of air in doping M element while not reducing material capacity, enhance the stability of battery.
Description
Technical field
The invention belongs to battery material technical fields, and in particular to a kind of positive electrode material precursor, and preparation method thereof and
Purposes.
Background technique
The critical material of secondary cell is positive electrode, and sodium-ion battery is no exception, and positive electrode cost is to determine sodium
One of the principal element of ion battery cost.Transition metal ions layered oxide ternary material is the novel sodium developed in recent years
Ion battery positive electrode has the advantages that at low cost, raw material sources are extensive, and specific capacity is moderate, great application potential.These are just
The sodium-ion battery that pole material is constituted would be possible to be applied to low side electric vehicle and extensive energy storage field.
Stratiform NaMnO2It is sodium-ion battery positive material studied earliest, research shows that this kind of material has O3 and P2
Two different crystal structures, and it is relatively stable.In view of deficiency existing for single metal oxides, comprehensive different monometallics
The advantage of individual and the research of multi-element metal oxide formed, basic goal exactly improve single metal oxides material
Unstability and the charge/discharge capacity for playing material further increase the specific volume and cycle performance of battery itself.It is wherein more prominent
Out be exactly Fe element and Ni element, Fe element can replace Mn element to a certain extent, and Lai Shixian is for stability of material
The further reinforcing of energy enables to the monometallic material specific volume of script to improve, just for battery instantly after with Fe element
For the material market of pole, development prospect is wide.But at the same time after it seriously affects the problem of moisture-sensitive
Continuous popularization, i.e., in the actual application process, there are certain difficulty.Ni element can improve anode to a certain extent
The stability of material, and it is capable of providing high-energy density not available for single metallic elements material, either specific volume or battery
In terms of capacity, also there is original performance, therefore, Ni is also widely used in stratiform NaMnO2Doping in.
Seung-Min Oh et al. has studied a kind of doping type Na [Ni0.25Fe0.5Mn0.25]O2/C-Fe3O4Sodium-ion battery,
The electrode material has good chemical property, and still, property stable in the air is very poor (referring to document " Advanced Na
[Ni0.25Fe0.5Mn0.25]O2/C-Fe3O4Sodium-Ion Batteries Using EMS Electrolyte for Energy
Storage”,Seung-Min Oh et al,Nano Lett,2014,14(3):1620-1626)。
CN109119610A discloses a kind of alkaline aqueous solution sodium-ion battery and preparation method thereof, the positive material used
Material is NaMnNO, and N is doped chemical, can be the metallic elements such as Ca, Ti, V, Cr, Mn, Fe ﹑ Co, Ni, Cu, Zn, Al ﹑ Zr, Ru
One or more of.The preparation process of the sodium-ion battery is simple, but the aerial stability of its positive electrode is poor,
Chemical property is poor.
CN107093713A discloses a kind of anion doped sodium-ion battery oxide anode material, the preparation side
Method includes the following steps: that (1) stoichiometrically mixes sodium source compound, M source compound, N source compound and Y source compound
It closes, 1~12h of ball milling mixing；(2) presoma is placed in Muffle furnace and calcines 3-24h under the conditions of 800~1300 DEG C, be cooled to
Room temperature obtains anion doped sodium-ion battery oxide anode material.The positive electrode that the method is prepared is in sky
Stability in gas is poor, and chemical property is poor.
Therefore, this field needs to develop a kind of novel anode material, keeps it with good stability in air, has
Good chemical property, and preparation process is simple, it can industrialized production.
Summary of the invention
In view of the deficiencies of the prior art, the purpose of the present invention is to provide a kind of positive electrode material precursor and its preparation sides
Method and purposes.
In order to achieve the above object, the invention adopts the following technical scheme:
One of the objects of the present invention is to provide a kind of positive electrode material precursor, the chemical formula of the positive electrode material precursor
For FeaMnbNicMd(OH)x, wherein 0<a<1,0<b<1,0<c<1, a+b+c>=0.90,0.01<d≤0.1, a+b+c+d=1,2<x
<3；Value of a such as 0.1,0.2,0.3,0.4,0.5,0.6,0.7,0.8 or 0.9 etc..The value of the b such as 0.1,
0.2,0.3,0.4,0.5,0.6,0.7,0.8 or 0.9 etc..The value of the c such as 0.1,0.2,0.3,0.4,0.5,0.6,
0.7,0.8 or 0.9 etc..The value of the a+b+c such as 0.91,0.92,0.93,0.94,0.95,0.96,0.97,0.98 or
0.99 etc..Value of the d such as 0.02,0.03,0.04,0.05,0.06,0.07,0.08 or 0.09 etc..The value of the x
Such as 2.1,2.2,2.3,2.4,2.5,2.6,2.7,2.8 or 2.9 etc..
The M includes the combination of any one in Al element, Cu element and Co element or at least two.
The present invention improves the interlamellar spacing of positive electrode material precursor by the way of adulterating M element, and then improves positive material
The structural stability of material precursor；Meanwhile before positive electrode can be effectively reduced while not reducing material capacity in doping M element
Body is driven to the sensibility of air, enhances the stability of battery.
In the chemical formula of positive electrode material precursor of the present invention when d≤0.01, before the doping of M element is for positive electrode
The structural stability promotion for driving body is smaller；As d > 0.1 in the chemical formula of the positive electrode material precursor, the doping of M element
Excessively, capacity is lower.
Preferably, the 0 < a < 0.33,0 <b < 0.33,0 < c < 0.33,0 < d < 0.05.
Preferably, the partial size of the positive electrode material precursor is 0.15~0.25 μm, such as 0.16 μm, 0.17 μm, 0.18 μ
M, 0.19 μm, 0.20 μm, 0.21 μm, 0.22 μm, 0.23 μm or 0.24 μm etc..
Preferably, the positive electrode material precursor is stratified material.
Preferably, the interlamellar spacing of the positive electrode material precursor be 0.4~1nm, such as 0.41nm, 0.45nm, 0.5nm,
0.6nm, 0.7nm, 0.8nm, 0.9nm etc..
The interlamellar spacing of positive electrode material precursor of the present invention is conducive to the reversible of sodium ion and take off/inlays, be conducive to sodium from
The storage of son, and then improve the cycle performance of material.
The second object of the present invention is to provide a kind of preparation method of positive electrode material precursor, and the preparation method includes
Following steps:
It will be mixed containing source of iron, manganese source, nickel source and the mixed solution in the source M with alkaline solution, heating obtains reaction and obtains just
Pole material precursor crude product.
Preferably, source of iron, manganese source, nickel source and the source M are carried out by the stoichiometric ratio of the chemical formula in the mixed solution
Configuration, the chemical formula are FeaMnbNicMd(OH)x, wherein 0<a<1,0<b<1,0<c<1, a+b+c>=0.90,0.01<d≤
0.1, a+b+c+d=1,2 < x < 3；
The M includes the combination of any one in Al element, Cu element and Co element or at least two.
Preferably, the source of iron includes any one in iron chloride, ferric nitrate, ferric carbonate and ferric sulfate or at least two
Combination, preferably sulfuric acid iron.
Preferably, the manganese source includes any one in manganese chloride, manganese nitrate, manganese sulfate and manganese acetate or at least two
Combination, preferably sulfuric acid manganese.
Preferably, the nickel source includes any one in nickel chloride, nickel nitrate, nickel acetate, nickel sulfate and nickel hydroxide
Or at least two combination, preferably sulfuric acid nickel.
Preferably, the source M include in the source Al, the source Cu and the source Co any one or at least two combination.
Preferably, the source Al includes any one in aluminum nitrate, aluminium carbonate, aluminum sulfate and aluminium chloride or at least two
Combination, preferably sulfuric acid aluminium.
Preferably, the source Cu includes any one in copper nitrate, copper carbonate, copper sulphate and copper chloride or at least two
Combination, preferably sulfuric acid copper.
Preferably, the source Co includes any one in cobalt nitrate, cobalt carbonate, cobaltous sulfate and cobalt chloride or at least two
Combination, preferably sulfuric acid cobalt.
Preferably, in the mixed solution metallic element total mol concentration be 0.5~2mol/L, such as 0.6mol/L,
0.8mol/L, 0.9mol/L, 1mol/L, 1.2mol/L, 1.4mol/L, 1.5mol/L, 1.6mol/L or 1.8mol/L etc..
Preferably, the alkaline solution includes sodium hydroxide and/or ammonium hydroxide, and the mixing of preferably sodium hydroxide and ammonium hydroxide is molten
Liquid.
Preferably, the ratio between mole hydroxy in the integral molar quantity and alkaline solution of metallic element in the mixed solution
For 1:2.1~3.0, such as 1:2.2,1:2.3,1:2.4,1:2.5,1:2.6,1:2.7,1:2.8 or 1:2.9 etc..
Preferably, in the alkaline solution sodium hydroxide content be 10~50wt%, such as 15wt%, 18wt%,
20wt%, 22wt%, 25wt%, 30wt%, 35wt%, 40wt% or 45wt% etc..
Preferably, in the alkaline solution ammonium hydroxide content be 1~3mol/L, such as 1.2mol/L, 1.5mol/L,
1.8mol/L, 2mol/L, 2.2mol/L, 2.5mol/L, 2.6mol/L, 2.8mol/L or 2.9mol/L etc..
Preferably, solvent is water in the alkaline solution.
Preferably, the hybrid mode of the mixed solution and alkaline solution are as follows: mixed solution is added dropwise in alkaline solution,
Stirring.
The present invention is in such a way that mixed solution is added dropwise in alkaline solution, obtained positive electrode material precursor uniform particle sizes
Property is more preferable；It is directly mixed according to the mode or mixed solution that alkaline solution is added dropwise in mixed solution with alkaline solution
The obtained positive electrode material precursor particle size uniformity of mode it is poor.
Preferably, the speed of the dropwise addition be 1~5mL/min, such as 1.5mL/min, 1.8mL/min, 2mL/min,
2.3mL/min, 2.5mL/min, 3mL/min, 3.2mL/min, 3.5mL/min, 4mL/min, 4.2mL/min, 4.5mL/min or
4.8mL/min waiting.
When the speed of dropwise addition is less than 1mL/min, rate of addition is excessively slow, and production efficiency is lower；When the speed of dropwise addition is greater than
When 5mL/min, rate of addition is too fast, little particle easily generated, in electrochemical reaction process, little particle can with electrolyte occur compared with
More side reactions, and then lead to the decaying of battery performance.
Preferably, the speed of the stirring is 600~1000rpm, such as 700rpm, 800rpm, 900rpm or 1000rpm
Deng.
Preferably, the time of the stirring is 1.5~2.5h, such as 1.6h, 1.8h, 2h, 2.2h or 2.4h etc..
Preferably, the temperature of the heating is 50~80 DEG C, such as 55 DEG C, 60 DEG C, 65 DEG C, 70 DEG C or 75 DEG C etc..
When the temperature of heating of the present invention is less than 50 DEG C, ionic reaction is incomplete, in obtained positive electrode material precursor
Activity substance content is lower, influences the chemical property of material；When the temperature of heating is greater than 80 DEG C, manganic and ferrous iron can quilts
It aoxidizes, activity substance content is lower in positive electrode material precursor obtained, influences the chemical property of material.
Preferably, the time of the heating is 1~7h, such as 2h, 3h, 4h, 5h or 6h etc..
Preferably, the atmosphere of the heating is protective atmosphere.
The atmosphere of heating of the present invention is protective atmosphere, prevents manganic in the synthesis process and ferrous iron by oxygen
Change, influences the chemical property of material.
Preferably, the protective atmosphere include in nitrogen atmosphere, argon atmosphere and helium atmosphere any one or extremely
Few two kinds of combination, preferably nitrogen atmosphere.
Preferably, the method also includes being post-processed to positive electrode material precursor crude product, the process of the post-processing
Including: successively to be cooled down to the positive electrode material precursor crude product, is separated by solid-liquid separation, washing to water lotion is neutral and drying,
Obtain positive electrode material precursor.
Preferably, the temperature of the drying is 80~120 DEG C, such as 85 DEG C, 90 DEG C, 95 DEG C, 100 DEG C, 105 DEG C, 110 DEG C
Or 115 DEG C etc..
Preferably, the time of the drying is 5~10h, such as 5.5h, 6h, 7h, 8h or 9h etc..
As optimal technical scheme, a kind of preparation method of positive electrode material precursor of the present invention includes the following steps:
(1) source of iron, manganese source, nickel source and the source M are configured in the ratio of the chemical formula, obtains mixed solution, it is described
The total mol concentration of metallic element is 0.5~2mol/L in mixed solution；
Wherein, the chemical formula is FeaMnbNicMd(OH)x, wherein 0<a<1,0<b<1,0<c<1, a+b+c>=0.90,
0.01 < d≤0.1, a+b+c+d=1,2 < x < 3；
The M includes the combination of any one in Al element, Cu element and Co element or at least two；
(2) step (1) described mixed solution is added dropwise in alkaline solution with the speed of 1~5mL/min, the alkalinity is molten
Liquid is the mixed solution of sodium hydroxide and ammonium hydroxide, hydrogen-oxygen in the integral molar quantity and alkaline solution of metallic element in the mixed solution
The ratio between mole of root is 1:2.1~3.0, and wherein the content of sodium hydroxide is 10~50wt%, the content of ammonium hydroxide is 1~
3mol/L stirs 1.5~2.5h with 600~1000rpm, and then in a nitrogen atmosphere, 50~80 DEG C of 1~7h of heating are obtained just
Pole material precursor crude product；
(3) step (2) the positive electrode material precursor crude product is successively cooled down, is separated by solid-liquid separation, washing to water lotion
For neutral and 80~120 DEG C of 5~10h of drying, positive electrode material precursor is obtained.
The third object of the present invention is to provide a kind of preparation method of positive electrode, and the preparation method includes: by mesh
One of described in positive electrode material precursor and sodium source mixing, obtain mixture, the mixture be sintered, obtain positive material
Material.
Relative to the method for being mixed with positive electrode using sodium source and source of iron, manganese source, nickel source and one step of the source M, the present invention
It is obtained just then by way of precursor synthesis positive electrode using the doping for carrying out M element in positive electrode material precursor
Pole material particle size is more uniform, and distribution of the M element in positive electrode is more uniform, obtained positive electrode air stability
Higher, chemical property is more preferable.
Preferably, the sodium source includes sodium carbonate.
Preferably, in the positive electrode material precursor and sodium source sodium element 0.95~1.05:1 of molar ratio, such as 0.96:
1,0.97:1,0.98:1,0.99:1,1:1,1.01:1,1.02:1,1.03:1 or 1.04:1.
Preferably, the temperature of the sintering is 800~1000 DEG C, such as 850 DEG C, 900 DEG C, 950 DEG C or 980 DEG C etc..
Preferably, the time of the sintering be 10~for 24 hours, such as 12h, 15h, 16h, 18h, 20h, 21h, 22h or 23h
Deng.
As optimal technical scheme, a kind of preparation method of positive electrode of the present invention, the preparation method includes such as
Lower step:
(1) source of iron, manganese source, nickel source and the source M are configured in the ratio of the chemical formula, obtains mixed solution, it is described
The total mol concentration of metallic element is 0.5~2mol/L in mixed solution；
Wherein, the chemical formula is FeaMnbNicMd(OH)x, wherein 0<a<1,0<b<1,0<c<1, a+b+c>=0.90,
0.01 < d≤0.1, a+b+c+d=1,2 < x < 3；
The M includes the combination of any one in Al element, Cu element and Co element or at least two；
(2) step (1) described mixed solution is added dropwise in alkaline solution with the speed of 1~5mL/min, the alkalinity is molten
Liquid is the mixed solution of sodium hydroxide and ammonium hydroxide, hydrogen-oxygen in the integral molar quantity and alkaline solution of metallic element in the mixed solution
The ratio between mole of root is 1:2.1~3.0, and wherein the content of sodium hydroxide is 10~50wt%, the content of ammonium hydroxide is 1~
3mol/L, 600~1000rpm stir 1.5~2.5h, and then in a nitrogen atmosphere, 50~80 DEG C of 1~7h of heating obtain anode
Material precursor crude product；
(3) step (2) the positive electrode material precursor crude product is successively cooled down, is separated by solid-liquid separation, washing to water lotion
For neutral and 80~120 DEG C of 5~10h of drying, positive electrode material precursor is obtained；
(4) by sodium element in step (3) positive electrode material precursor and sodium carbonate, 0.95~1.05:1 is mixed in molar ratio
Close, obtain mixture, by the mixture carry out 800~1000 DEG C sintering 10~for 24 hours, obtain positive electrode.
The fourth object of the present invention is to provide a kind of positive electrode, and the positive electrode passes through one kind described in the third purpose
The preparation method of positive electrode obtains.
Preferably, the positive electrode is stratified material.
Preferably, the interlamellar spacing of the positive electrode be 0.40~1nm, such as 0.41nm, 0.45nm, 0.5nm, 0.6nm,
0.7nm, 0.8nm, 0.9nm etc..
Preferably, the partial size of the positive electrode be 0.3~0.5 μm, such as 0.32 μm, 0.35 μm, 0.38 μm, 0.4 μm,
0.42 μm, 0.44 μm, 0.45 μm, 0.46 μm or 0.48 μm etc..
The fifth object of the present invention is to provide a kind of sodium-ion battery, and the sodium-ion battery includes described in the fourth purpose
Positive electrode.
Preferably, positive electrode described in four for the purpose of the sodium-ion battery positive material.
Compared with prior art, the invention has the following beneficial effects:
(1) present invention improves the interlamellar spacing of positive electrode material precursor by the way of adulterating M element, and then improves anode
The structural stability of material precursor；Meanwhile positive electrode can be effectively reduced in doping M element while not reducing material capacity
Presoma enhances the stability of battery to the sensibility of air.
(2) relative to the method for being mixed with positive electrode using sodium source and source of iron, manganese source, nickel source and one step of the source M, originally
Invention is obtained then by way of precursor synthesis positive electrode using the doping for carrying out M element in positive electrode material precursor
It is more uniform to positive electrode partial size, and distribution of the M element in positive electrode is more uniform, obtained positive electrode air is steady
Qualitative higher, chemical property is more preferable.
Detailed description of the invention
Fig. 1 is the SEM figure for the positive electrode material precursor that the specific embodiment of the invention 1 obtains；
Fig. 2 is the positive electrode SEM figure that the specific embodiment of the invention 1 obtains；
Fig. 3 is the SEM figure after the positive electrode that the specific embodiment of the invention 1 obtains is placed one month in air；
Fig. 4 is the positive electrode and its XRD diagram after placing one month in air that the specific embodiment of the invention 1 obtains；
Fig. 5 is the SEM figure for the positive electrode material precursor that specific comparative example 1 of the invention obtains；
Fig. 6 is the positive electrode SEM figure that specific comparative example 1 of the invention obtains；
Fig. 7 is the SEM figure after the positive electrode that specific comparative example 1 of the invention obtains is placed one month in air；
Fig. 8 is the positive electrode and its XRD diagram after placing one month in air that specific comparative example 1 of the invention obtains.
Specific embodiment
Of the invention for ease of understanding, it is as follows that the present invention enumerates embodiment.Those skilled in the art are it will be clearly understood that the implementation
Example is only to aid in the understanding present invention, should not be regarded as a specific limitation of the invention.
Embodiment 1
A kind of preparation method of positive electrode includes the following steps:
(1) iron chloride, manganese chloride, nickel chloride and aluminium chloride are pressed into Fe0.32Mn0.33Ni0.33Al0.02(OH)2.1Chemical formula
Ratio is configured, and mixed solution is obtained, and the total mol concentration of metallic element is 1mol/L in the mixed solution；
(2) step (1) described mixed solution is added dropwise in alkaline solution with the speed of 2mL/min, the alkaline solution
For the mixed solution of sodium hydroxide and ammonium hydroxide, hydroxyl in the integral molar quantity and alkaline solution of metallic element in the mixed solution
The ratio between mole be 1:2.4, wherein the content of sodium hydroxide is 30wt%, and the content of ammonium hydroxide is 2mol/L, 800rpm stirring
2.4h, then in a nitrogen atmosphere, 55 DEG C of heating 3h obtain positive electrode material precursor crude product；
(3) step (2) the positive electrode material precursor crude product is successively cooled down, is separated by solid-liquid separation, washing to water lotion
For neutral and 100 DEG C of drying 8h, obtain positive electrode material precursor, the SEM of the positive electrode material precursor scheme as shown in Figure 1, by
As can be seen that positive electrode material precursor is stratified material in figure, particle size uniformity is good, and partial size is 0.2 μm；
(4) in molar ratio it is that 1:1 is mixed by sodium element in step (3) positive electrode material precursor and sodium carbonate, obtains
The mixture is carried out 900 DEG C of sintering 20h, obtains positive electrode by mixture.The SEM of the positive electrode schemes such as Fig. 2 institute
Show, as can be seen from Figure, positive electrode is stratified material, and particle size uniformity is good, and partial size is 0.4 μm；By the positive electrode
SEM figure after placing one month in air as shown in figure 3, as can be seen from Figure, cathode material structure is unchanged, surface without
Obvious dendrite generates, and illustrates that the positive electrode is aerial and has good stability；Fig. 4 is for the positive electrode with it in air
It is middle place one month after XRD diagram, as can be seen from Figure, the positive electrode place in air one month after with before placement
It is not substantially change compared to crystal structure, demonstrates that the positive electrode is aerial to have good stability.
Embodiment 2
The difference from embodiment 1 is that aluminium chloride replaces with copper chloride in step (1).
Embodiment 3
The difference from embodiment 1 is that the temperature heated in step (2) is 50 DEG C.
Embodiment 4
The difference from embodiment 1 is that the temperature heated in step (2) is 80 DEG C.
Embodiment 5
The difference from embodiment 1 is that the temperature heated in step (2) is 40 DEG C.
Embodiment 6
The difference from embodiment 1 is that the temperature heated in step (2) is 90 DEG C.
Embodiment 7
The difference from embodiment 1 is that the integral molar quantity of metallic element and alkalinity are molten in mixed solution described in step (2)
The ratio between mole hydroxy is 1:2.1 in liquid.
Embodiment 8
The difference from embodiment 1 is that the integral molar quantity of metallic element and alkalinity are molten in mixed solution described in step (2)
The ratio between mole hydroxy is 1:3.0 in liquid.
Embodiment 9
The difference from embodiment 1 is that the integral molar quantity of metallic element and alkalinity are molten in mixed solution described in step (2)
The ratio between mole hydroxy is 1:2 in liquid.
Embodiment 10
The difference from embodiment 1 is that the integral molar quantity of metallic element and alkalinity are molten in mixed solution described in step (2)
The ratio between mole hydroxy is 1:3.1 in liquid.
Embodiment 11
The difference from embodiment 1 is that the alkaline solution is added dropwise to mixing with the speed of 2mL/min in step (2)
In solution.
Embodiment 12
The difference from embodiment 1 is that the mixed solution is added dropwise to alkalinity with the speed of 6mL/min in step (2)
In solution.
Embodiment 13
A kind of preparation method of positive electrode includes the following steps:
(1) ferric nitrate, manganese nitrate, nickel nitrate and aluminum nitrate are pressed into Fe0.32Mn0.32Ni0.32Al0.04(OH)2.2Chemical formula
Ratio is configured, and mixed solution is obtained, and the total mol concentration of metallic element is 0.5mol/L in the mixed solution；
(2) step (1) described mixed solution is added dropwise in alkaline solution with the speed of 1mL/min, the alkaline solution
For the mixed solution of sodium hydroxide and ammonium hydroxide, hydroxyl in the integral molar quantity and alkaline solution of metallic element in the mixed solution
The ratio between mole be 1:2.4, wherein the content of sodium hydroxide is 50wt%, and the content of ammonium hydroxide is 1mol/L, 600rpm stirring
1.5h, then under helium atmosphere, 80 DEG C of heating 1h obtain positive electrode material precursor crude product；
(3) step (2) the positive electrode material precursor crude product is successively cooled down, is separated by solid-liquid separation, washing to water lotion
For neutral and 80 DEG C of drying 10h, positive electrode material precursor is obtained；
(4) by sodium element in step (3) positive electrode material precursor and sodium carbonate, 0.95:1 is mixed in molar ratio, is obtained
The mixture is carried out 1000 DEG C of sintering 10h, obtains positive electrode by mixture.
Embodiment 14
A kind of preparation method of positive electrode includes the following steps:
(1) iron chloride, manganese chloride, nickel chloride and aluminium chloride are pressed into Fe0.32Mn0.31Ni0.31Al0.06(OH)2.1Chemical formula
Ratio is configured, and mixed solution is obtained, and the total mol concentration of metallic element is 2mol/L in the mixed solution；
(2) step (1) described mixed solution is added dropwise in alkaline solution with the speed of 5mL/min, the alkaline solution
For the mixed solution of sodium hydroxide and ammonium hydroxide, hydroxyl in the integral molar quantity and alkaline solution of metallic element in the mixed solution
The ratio between mole be 1:2.4, wherein the content of sodium hydroxide is 10wt%, and the content of ammonium hydroxide is 3mol/L, 800rpm stirring
2.5h, then in a nitrogen atmosphere, 50 DEG C of heating 7h obtain positive electrode material precursor crude product；
(3) step (2) the positive electrode material precursor crude product is successively cooled down, is separated by solid-liquid separation, washing to water lotion
For neutral and 120 DEG C of drying 5h, positive electrode material precursor is obtained；
(4) by sodium element in step (3) positive electrode material precursor and sodium carbonate, 1.05:1 is mixed in molar ratio, is obtained
The mixture is carried out 800 DEG C of sintering for 24 hours, obtains positive electrode by mixture.
Comparative example 1
The difference from embodiment 1 is that not adding aluminium chloride in step (1), obtained positive electrode material precursor is Fe1/ 3Mn1/3Ni1/3(OH)2, obtained positive electrode is Na1.00Fe1/3Ni1/3Mn1/3O2, the SEM figure of the positive electrode material precursor is such as
Shown in Fig. 5, as can be seen from Figure, positive electrode material precursor is stratified material, and partial size is 0.2 μm；The SEM of the positive electrode
As shown in fig. 6, as can be seen from Figure, positive electrode is stratified material, and interlamellar spacing is smaller, and uniform particle sizes are poor, partial size is figure
0.6μm；SEM figure after the positive electrode is placed one month in air is as shown in fig. 7, as can be seen from Figure, anode
Material structure has significant change, and there is dendrite generation on surface, and dendrite ingredient is sodium carbonate or sodium bicarbonate, illustrates the positive electrode
Aerial stability is poor；Fig. 8 is the positive electrode and its XRD diagram after placing one month in air, You Tuzhong
As can be seen that the positive electrode is substantially change before placing compared to crystal structure after placing in air one month, card
The bright aerial stability of the positive electrode is poor.
Comparative example 2
The difference from embodiment 1 is that aluminium chloride replaces with titanium chloride in step (1), obtained presoma is
Fe0.32Mn0.33Ni0.33Ti0.02(OH)2.1。
Comparative example 3
The difference from embodiment 1 is that iron chloride, manganese chloride, nickel chloride and aluminium chloride are pressed in step (1)
Fe0.335Mn0.33Ni0.33Al0.005(OH)2.1The ratio of chemical formula is configured.
Comparative example 4
The difference from embodiment 1 is that iron chloride, manganese chloride, nickel chloride and aluminium chloride are pressed in step (1)
Fe0.34Mn0.23Ni0.23Al0.2(OH)2.1The ratio of chemical formula is configured.
Performance test:
The positive electrode being prepared is performed the following performance tests:
(1) battery assembly: positive electrode produced by the present invention is named as A, by positive electrode produced by the present invention in sky
A month obtained positive electrode to be placed in gas and is named as B, and anode pole piece is respectively prepared in A and B, cathode is metallic sodium piece, every
Film is Celgard2400, and electrolyte is the sodium perchlorate of 1mol/L, is assembled into CR2025 type button cell.The system of anode pole piece
Standby process includes: by positive electrode A or B, conductive agent acetylene black, binder CMC (sodium carboxymethylcellulose) according to 80:10:10
Mass ratio, be mixed after slurry and be coated on aluminium foil with water as solvent, 120 DEG C after drying 12 hours, are rolled and are punched into
Diameter is the disk of 8.4mm as anode pole piece.
(2) electro-chemical test: in normal temperature condition, button cell obtained is surveyed on LAND battery test system
Examination, charging/discharging voltage section are 2~4V, and definition 1C current density is 130mA/g, and A first discharge specific capacity and B discharge ratio for the first time
Capacity respectively represents the first discharge specific capacity of A material and B material；Coulombic efficiency respectively represents A for the first time by coulombic efficiency and B for the first time
The coulombic efficiency for the first time of A material and B material；30 weeks circulation volumes for respectively representing A material and B material for A-30 weeks and B-30 weeks are protected
Holdup；The 30 weeks circulation volume conservation rates=specific discharge capacity/first discharge specific capacity of circulation 30 weeks, for the first time coulombic efficiency=for the first time
Specific discharge capacity/initial charge specific capacity.
Table 1
It can be seen from Table 1 that the positive electrode chemical property that the embodiment of the present invention 1~14 obtains is good, A is put for the first time
Electric specific capacity >=114mAh/g, A coulombic efficiency >=88.45%, A-30 week >=75.51% for the first time；By the positive electrode in sky
It places one month and is tested in gas, chemical property is equally good, B first discharge specific capacity >=112mAh/g, B coulomb for the first time
Efficiency >=88.25%, B-30 week >=75.38%, A and B performance are not much different, and the positive electrode air stability illustrated is good
It is good.
It can be seen from Table 1 that embodiment 5 is relative to embodiment 1, A first discharge specific capacity, A coulombic efficiency, A- for the first time
30 weeks, B first discharge specific capacity, B coulombic efficiency and B-30 weeks smaller for the first time, it may be possible to because of the temperature heated in embodiment 5
Too low, leading to precipitating, not exclusively positive active material is less and obtained positive electrode uniformity is poor, so 5 phase of embodiment
For embodiment 1, A first discharge specific capacity, A for the first time coulombic efficiency, A-30 weeks, B first discharge specific capacity, B for the first time imitate by coulomb
Rate and B-30 weeks smaller.
It can be seen from Table 1 that embodiment 6 is relative to embodiment 1, A first discharge specific capacity, A coulombic efficiency, A- for the first time
30 weeks, B first discharge specific capacity, B coulombic efficiency and B-30 weeks smaller for the first time, it may be possible to because of the temperature heated in embodiment 6
It is excessively high, cause manganic and ferrous iron to be oxidized, the active material that electrochemical reaction occurs is reduced, so applying example 6 relative to reality
Apply example 1, A first discharge specific capacity, A coulombic efficiency, A-30 weeks, B first discharge specific capacity, B coulombic efficiency and B- for the first time for the first time
It is 30 weeks smaller.
It can be seen from Table 1 that embodiment 9 is relative to embodiment 1, A first discharge specific capacity, A coulombic efficiency, A- for the first time
30 weeks, B first discharge specific capacity, B coulombic efficiency and B-30 weeks smaller for the first time, it may be possible to because in embodiment 9 in mixed solution
The ratio between mole hydroxy is 1:2 in the integral molar quantity and alkaline solution of metallic element, and content hydroxy is too low, leads to Al
Element cannot precipitate completely, influence the chemical property of material, so embodiment 9 is relative to embodiment 1, A discharges specific volume for the first time
Amount, A coulombic efficiency, A-30 weeks, B first discharge specific capacity, B coulombic efficiency and B-30 weeks smaller for the first time for the first time.
It can be seen from Table 1 that embodiment 10 is relative to embodiment 1, A first discharge specific capacity, A for the first time coulombic efficiency,
A-30 weeks, B first discharge specific capacity, B coulombic efficiency and B-30 weeks smaller for the first time, it may be possible to because of mixed solution in embodiment 10
The ratio between mole hydroxy is 1:3.1 in the integral molar quantity and alkaline solution of middle metallic element, and too high levels hydroxy are led
It causes Al element that cannot precipitate completely, influences the chemical property of material, so embodiment 10 is relative to embodiment 1, A discharges for the first time
Specific capacity, A coulombic efficiency, A-30 weeks, B first discharge specific capacity, B coulombic efficiency and B-30 weeks smaller for the first time for the first time.
It can be seen from Table 1 that embodiment 11 is relative to embodiment 1, A first discharge specific capacity, A for the first time coulombic efficiency,
A-30 weeks, B first discharge specific capacity, B coulombic efficiency and B-30 weeks smaller for the first time, it may be possible to because in embodiment 11 will alkalinity it is molten
Drop adds in mixed solution, and the granularity of material goes up comparatively fast, and granularity is more difficult to control, the particle of larger granularity easily generated, and big
Broken, dusting and disengaging easily occur in electrochemical reaction process for grain, the chemical property of material are influenced, so 11 phase of embodiment
For embodiment 1, A first discharge specific capacity, A for the first time coulombic efficiency, A-30 weeks, B first discharge specific capacity, B for the first time imitate by coulomb
Rate and B-30 weeks smaller.
It can be seen from Table 1 that embodiment 12 is relative to embodiment 1, A first discharge specific capacity, A for the first time coulombic efficiency,
A-30 weeks, B first discharge specific capacity, B coulombic efficiency and B-30 weeks smaller for the first time, it may be possible to because of mixed solution in embodiment 12
It is added dropwise in alkaline solution with the speed of 6mL/min, rate of addition is too fast, and system nucleation is very fast, fine particle easily generated, in electricity
With electrolyte more side reaction can occur for chemical reaction process small particles, and then lead to the decaying of battery performance, so implementing
Example 12 relative to embodiment 1, A first discharge specific capacity, A for the first time coulombic efficiency, A-30 weeks, B first discharge specific capacity, B for the first time
Coulombic efficiency and B-30 weeks smaller.
It can be seen from Table 1 that comparative example 1 is relative to embodiment 1, A first discharge specific capacity, A coulombic efficiency, A- for the first time
30 weeks, B first discharge specific capacity, B coulombic efficiency and B-30 weeks smaller for the first time, it may be possible to because not adding chlorination in comparative example 1
Aluminium, the positive electrode interlamellar spacing obtained from is smaller, is unfavorable for the storage of sodium ion, so comparative example 1 is relative to embodiment 1, A
First discharge specific capacity, A for the first time coulombic efficiency, A-30 weeks, B first discharge specific capacity, B for the first time coulombic efficiency and B-30 weeks compared with
It is small；Meanwhile relative to embodiment 1, comparative example 1 place in air one month front and back obtain positive electrode performance difference compared with
Greatly, illustrate that the doping of Al element improves the aerial stability of positive electrode.
It can be seen from Table 1 that comparative example 2 is relative to embodiment 1, A first discharge specific capacity, A coulombic efficiency, A- for the first time
30 weeks, B first discharge specific capacity, B coulombic efficiency and B-30 weeks smaller for the first time, it may be possible to because of aluminium chloride replacement in comparative example 2
For titanium chloride, titanium elements are smaller to the castering action of positive electrode interlamellar spacing, are unfavorable for the storage of sodium ion, so comparative example 2
Relative to embodiment 1, A first discharge specific capacity, A coulombic efficiency, A-30 weeks, B first discharge specific capacity, B coulomb for the first time for the first time
Efficiency and B-30 weeks smaller；Meanwhile relative to embodiment 1, comparative example 1 places the positive material that a month front and back obtains in air
Expect that performance difference is larger, illustrates that, relative to Al element, the promotion of the doping of titanium elements property stable in the air to positive electrode is made
With smaller.
It can be seen from Table 1 that comparative example 3 is relative to embodiment 1, A first discharge specific capacity, A coulombic efficiency, A- for the first time
30 weeks, B first discharge specific capacity, B coulombic efficiency and B-30 weeks smaller for the first time, it may be possible to because being pressed in comparative example 3
Fe0.335Mn0.33Ni0.33Al0.005(OH)2.1The ratio of chemical formula is configured, the content mistake of Al element in obtained positive electrode
It is few and then smaller to the castering action of positive electrode interlamellar spacing, it is unfavorable for the storage of sodium ion, so comparative example 3 is relative to reality
Apply example 1, A first discharge specific capacity, A coulombic efficiency, A-30 weeks, B first discharge specific capacity, B coulombic efficiency and B- for the first time for the first time
It is 30 weeks smaller；Meanwhile relative to embodiment 1, comparative example 3 places the positive electrode performance phase that a month front and back obtains in air
Difference is larger, illustrates that the castering action of the too low property stable in the air for positive electrode of Al constituent content is smaller.
It can be seen from Table 1 that comparative example 4 is relative to embodiment 1, A first discharge specific capacity and B first discharge specific capacity
It is smaller, it may be possible to because pressing Fe in comparative example 40.34Mn0.23Ni0.23Al0.2(OH)2.1The ratio of chemical formula is configured, and then
To positive electrode in Al element content it is excessive, due to Al do not have electro-chemical activity cause capacity to reduce, so comparative example 4
Relative to embodiment 1, A first discharge specific capacity and B first discharge specific capacity are smaller.
The Applicant declares that the present invention is explained by the above embodiments detailed process equipment and process flow of the invention,
But the present invention is not limited to the above detailed process equipment and process flow, that is, it is above-mentioned detailed not mean that the present invention must rely on
Process equipment and process flow could be implemented.It should be clear to those skilled in the art, any improvement in the present invention,
Addition, selection of concrete mode of equivalence replacement and auxiliary element to each raw material of product of the present invention etc., all fall within of the invention
Within protection scope and the open scope.
Claims (10)
1. a kind of positive electrode material precursor, which is characterized in that the chemical formula of the positive electrode material precursor is FeaMnbNicMd
(OH)x, wherein 0<a<1,0<b<1,0<c<1, a+b+c>=0.90,0.01<d≤0.1, a+b+c+d=1,2<x<3；
The M includes the combination of any one in Al element, Cu element and Co element or at least two.
2. positive electrode material precursor as described in claim 1, which is characterized in that the 0 < a < 0.33,0 <b < 0.33,0 < c <
0.33,0 < d < 0.05；
Preferably, the partial size of positive electrode material precursor is 0.15~0.25 μm；
Preferably, the positive electrode material precursor is stratified material；
Preferably, the interlamellar spacing of the positive electrode material precursor is 0.4~1nm.
3. a kind of preparation method of positive electrode material precursor as claimed in claim 1 or 2, which is characterized in that the preparation method
Include the following steps:
It will be mixed containing source of iron, manganese source, nickel source and the mixed solution in the source M with alkaline solution, heating obtains reaction and obtains positive material
Material precursor crude product.
4. preparation method as claimed in claim 3, which is characterized in that source of iron, manganese source, nickel source and the source M in the mixed solution
It is configured by the stoichiometric ratio of the chemical formula, the chemical formula is FeaMnbNicMd(OH)x, wherein 0 < a < 1,0 <b < 1,0
<c<1, a+b+c>=0.90,0.01<d≤0.1, a+b+c+d=1,2<x<3；
The M includes the combination of any one in Al element, Cu element and Co element or at least two；
Preferably, the source of iron include in iron chloride, ferric nitrate, ferric carbonate and ferric sulfate any one or at least two group
It closes, preferably sulfuric acid iron；
Preferably, the manganese source include in manganese chloride, manganese nitrate, manganese sulfate and manganese acetate any one or at least two group
It closes, preferably sulfuric acid manganese；
Preferably, the nickel source include in nickel chloride, nickel nitrate, nickel acetate, nickel sulfate and nickel hydroxide any one or extremely
Few two kinds of combination, preferably sulfuric acid nickel；
Preferably, the source M include in the source Al, the source Cu and the source Co any one or at least two combination；
Preferably, the source Al include in aluminum nitrate, aluminium carbonate, aluminum sulfate and aluminium chloride any one or at least two group
It closes, preferably sulfuric acid aluminium；
Preferably, the source Cu include in copper nitrate, copper carbonate, copper sulphate and copper chloride any one or at least two group
It closes, preferably sulfuric acid copper；
Preferably, the source Co include in cobalt nitrate, cobalt carbonate, cobaltous sulfate and cobalt chloride any one or at least two group
It closes, preferably sulfuric acid cobalt；
Preferably, the total mol concentration of metallic element is 0.5~2mol/L in the mixed solution；
Preferably, the alkaline solution includes sodium hydroxide and/or ammonium hydroxide, the preferably mixed solution of sodium hydroxide and ammonium hydroxide；
Preferably, the ratio between mole hydroxy is 1 in the integral molar quantity and alkaline solution of metallic element in the mixed solution:
2.1~3.0；
Preferably, the content of sodium hydroxide is 10~50wt% in the alkaline solution；
Preferably, the content of ammonium hydroxide is 1~3mol/L in the alkaline solution；
Preferably, solvent is water in the alkaline solution；
Preferably, the hybrid mode of the mixed solution and alkaline solution are as follows: mixed solution is added dropwise in alkaline solution, is stirred
It mixes；
Preferably, the speed of the dropwise addition is 1~5mL/min；
Preferably, the speed of the stirring is 600~1000rpm；
Preferably, the time of the stirring is 1.5~2.5h.
5. preparation method as described in claim 3 or 4, which is characterized in that the temperature of the heating is 50~80 DEG C；
Preferably, the time of the heating is 1~7h；
Preferably, the atmosphere of the heating is protective atmosphere；
Preferably, the protective atmosphere includes any one in nitrogen atmosphere, argon atmosphere and helium atmosphere or at least two
The combination of kind, preferably nitrogen atmosphere；
Preferably, the method also includes post-processing to positive electrode material precursor crude product, the process of the post-processing includes:
The positive electrode material precursor crude product is successively cooled down, is separated by solid-liquid separation, washing to water lotion is neutral and drying, is obtained just
Pole material precursor；
Preferably, the temperature of the drying is 80~120 DEG C；
Preferably, the time of the drying is 5~10h.
6. the preparation method as described in one of claim 3-5, which is characterized in that the preparation method includes the following steps:
(1) source of iron, manganese source, nickel source and the source M are configured in the ratio of the chemical formula, obtains mixed solution, the mixing
The total mol concentration of GOLD FROM PLATING SOLUTION category element is 0.5~2mol/L；
Wherein, the chemical formula is FeaMnbNicMd(OH)x, wherein 0<a<1,0<b<1,0<c<1, a+b+c>=0.90,0.01<d
≤ 0.1, a+b+c+d=1,2 < x < 3；
The M includes the combination of any one in Al element, Cu element and Co element or at least two；
(2) step (1) described mixed solution is added dropwise in alkaline solution with the speed of 1~5mL/min, the alkaline solution is
The mixed solution of sodium hydroxide and ammonium hydroxide, it is hydroxy in the integral molar quantity and alkaline solution of metallic element in the mixed solution
The ratio between mole is 1:2.1~3.0, and wherein the content of sodium hydroxide is 10~50wt%, and the content of ammonium hydroxide is 1~3mol/L,
1.5~2.5h, then in a nitrogen atmosphere, 50~80 DEG C of 1~7h of heating, before obtaining positive electrode are stirred with 600~1000rpm
Drive body crude product；
(3) step (2) the positive electrode material precursor crude product is successively cooled down, is separated by solid-liquid separation, during washing to water lotion is
Property and 80~120 DEG C of 5~10h of drying, obtain positive electrode material precursor.
7. a kind of preparation method of positive electrode, which is characterized in that the preparation method include: by it is as claimed in claim 1 or 2 just
Pole material precursor and sodium source mixing, obtain mixture, the mixture are sintered, positive electrode is obtained；
Preferably, the sodium source includes sodium carbonate；
Preferably, the molar ratio of sodium element is 0.95~1.05 in the positive electrode material precursor and sodium source；
Preferably, the temperature of the sintering is 800~1000 DEG C；
Preferably, the time of the sintering be 10~for 24 hours.
8. preparation method as claimed in claim 7, which is characterized in that the preparation method includes the following steps:
(1) source of iron, manganese source, nickel source and the source M are configured in the ratio of the chemical formula, obtains mixed solution, the mixing
The total mol concentration of GOLD FROM PLATING SOLUTION category element is 0.5~2mol/L；
Wherein, the chemical formula is FeaMnbNicMd(OH)x, wherein 0<a<1,0<b<1,0<c<1, a+b+c>=0.90,0.01<d
≤ 0.1, a+b+c+d=1,2 < x < 3；
The M includes the combination of any one in Al element, Cu element and Co element or at least two；
(2) step (1) described mixed solution is added dropwise in alkaline solution with the speed of 1~5mL/min, the alkaline solution is
The mixed solution of sodium hydroxide and ammonium hydroxide, it is hydroxy in the integral molar quantity and alkaline solution of metallic element in the mixed solution
The ratio between mole is 1:2.1~3.0, and wherein the content of sodium hydroxide is 10~50wt%, and the content of ammonium hydroxide is 1~3mol/L,
600~1000rpm stirs 1.5~2.5h, and then in a nitrogen atmosphere, 50~80 DEG C of 1~7h of heating obtain positive electrode forerunner
Body crude product；
(3) step (2) the positive electrode material precursor crude product is successively cooled down, is separated by solid-liquid separation, during washing to water lotion is
Property and 80~120 DEG C of 5~10h of drying, obtain positive electrode material precursor；
(4) by sodium element in step (3) positive electrode material precursor and sodium carbonate, 0.95~1.05:1 is mixed in molar ratio, is obtained
To mixture, the mixture is subjected to 800~1000 DEG C of sintering 10~for 24 hours, obtains positive electrode.
9. a kind of positive electrode, which is characterized in that the positive electrode passes through a kind of positive electrode of claim 7 or 8
Preparation method obtains；
Preferably, the positive electrode is stratified material；
Preferably, the interlamellar spacing of the positive electrode is 0.40~1nm；
Preferably, the partial size of the positive electrode is 0.3~0.5 μm.
10. a kind of sodium-ion battery, which is characterized in that the sodium-ion battery includes positive electrode as claimed in claim 9；
Preferably, the sodium-ion battery positive material is positive electrode as claimed in claim 9.
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| CN116354417A (en) * | 2023-04-19 | 2023-06-30 | 荆门市格林美新材料有限公司 | Sodium ion precursor material and preparation method and application thereof |
| CN118479568A (en) * | 2024-07-15 | 2024-08-13 | 帕瓦(兰溪)新能源科技有限公司 | Quaternary precursor material, preparation method thereof and preparation method of positive electrode material |
| CN118479568B (en) * | 2024-07-15 | 2024-10-25 | 帕瓦(兰溪)新能源科技有限公司 | Quaternary precursor material, preparation method thereof and preparation method of positive electrode material |
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