CN108963233B - A kind of sodium-ion battery Cu-Fe-Mn layered oxide presoma and its preparation method and application - Google Patents
A kind of sodium-ion battery Cu-Fe-Mn layered oxide presoma and its preparation method and application Download PDFInfo
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Abstract
The present invention provides a kind of sodium-ion battery Cu-Fe-Mn layered oxide presoma and its preparation method and application, the preparation method of Cu-Fe-Mn layered oxide presoma includes: (1) by copper source, source of iron, manganese source and optionally the source metal M according to preset ratio is prepared into mixed liquor；(2) in protective atmosphere, mixed liquor, sodium hydroxide solution and ammonium hydroxide is mixed simultaneously and reacted, reaction product is obtained；(3) reaction product obtained by step (2) is post-processed, obtains Cu-Fe-Mn layered oxide presoma.The preparation method is simple, and product morphology is adjustable, can be used for preparing sodium-ion battery positive material, and electrochemical performance.
Description
Technical field
The invention belongs to battery technology field, be related to a kind of Cu-Fe-Mn layered oxide presoma and preparation method thereof and
Purposes more particularly to a kind of sodium-ion battery Cu-Fe-Mn layered oxide presoma and its preparation method and application.
Background technique
The critical material of sodium-ion battery is positive electrode, cost be determine sodium-ion battery cost principal element it
One.Three/quaternary material of layered oxide copper and iron manganese/nickel sodium salt is the novel anode material for the sodium-ion battery developed in recent years
Material has the advantages that at low cost, raw material sources are extensive, and specific capacity is moderate, good cycle.Good comprehensive performance, so that this
Three/quaternary material of a little copper and iron manganese/nickel is great application potential.The sodium-ion battery that these positive electrodes are constituted would be possible to answer
For low side electric vehicle and extensive energy storage field.
Fang Yongjin et al. report sodium-ion battery positive material progress (Acta Phys.-Chim.Sin.2017,
33 (1), 211-241), the positive electrode system of the current sodium-ion battery research of detailed overview, including transiting metal oxidation
Object, polyanion class material, Prussian-blue, organic molecule and polymer, non-crystalline material etc., and combine oneself project
Research work of the group in terms of anode, has inquired into the structure of material and the relationship of chemical property, analyzes raising positive electrode
Reversible capacity, voltage, structural stability possible approaches.Transition metal oxide material can use NaxMeO2It indicates, wherein Me
For transition metal, one or more of the elements such as including Mn, Fe, Ni, Co, V, Cu, Cr；X is the stoichiometric number of sodium, range
For 0 < x≤1.Different according to the structure of material, transition metal oxide can be divided into tunnel type oxide and layered oxide.
The preparation of three/quaternary material copper and iron manganese/nickel sodium salt layered oxide mainly uses high-temperature roasting method, presoma at present
For the oxide of various metals, there are preparation cost height, product is inhomogenous, it is difficult to the features such as controlling pattern.
Coprecipitation has product uniform, is easy to regulate and control pattern, at low cost, less cost of power, such as lithium ion battery
With ternary material nickel cobalt manganese, production is presently mainly to use to control crystalline co-precipitate method by complexing agent of ammonium hydroxide under protective atmosphere
Obtain the hydroxide precursor of nickel cobalt manganese.However, be not related in lithium ion battery ternary material nickel cobalt manganese copper and
Iron, because Cu is easily formed cupric ammine complex and co-precipitation is caused to fail under ammonium hydroxide existence condition；And Fe, if it is Fe3+,
The pH of precipitating is lower, easily prior to other precipitated metals, leads to co-precipitated materials distributing inhomogeneity, directly affects chemical property,
And if it is Fe2+, it is necessary to inert gas shielding is used, it is prevented to be oxidized to Fe in co-precipitation3+, so not having still at present
Report is in relation to the co-precipitation scheme containing metal ions such as copper, iron.
Three/quaternary material copper and iron manganese/nickel sodium salt layered oxide presoma preparation method is urgently improved.
Summary of the invention
In view of the deficiencies of the prior art, the present invention intends to provide a kind of sodium-ion battery Cu-Fe-Mn layers
Shape oxide precursor and its preparation method and application, the Cu-Fe-Mn layered oxide precursor preparation method is simple, easily
In operation, the Cu-Fe-Mn layered oxide presoma of different-shape can be obtained, the sodium-ion battery anode material prepared with it
Material, electrochemical performance.
To achieve this purpose, the present invention adopts the following technical scheme:
It is described one of the objects of the present invention is to provide a kind of preparation method of Cu-Fe-Mn layered oxide presoma
The chemical general formula of Cu-Fe-Mn layered oxide presoma is CuxFeyMzMn1-x-y-z(OH)2, wherein 0 < x < 1,0 < y < 1,0≤z <
1, M is selected from metallic element, and the preparation method includes the following steps:
(1) copper source, source of iron and manganese source are prepared into mixed liquor according to preset ratio；Or, by copper source, source of iron and manganese source and gold
Belong to the source M and is prepared into mixed liquor according to preset ratio；
(2) in protective atmosphere, mixed liquor, sodium hydroxide solution and ammonium hydroxide are mixed and is reacted simultaneously, is obtained
Reaction product；
(3) reaction product obtained by step (2) is post-processed, obtains Cu-Fe-Mn layered oxide presoma.
In the chemical general formula of the Cu-Fe-Mn layered oxide presoma value of x can for 0.1,0.2,0.3,0.4,
0.5, the value of 0.7 or 0.9 etc., y can be 0.1,0.2,0.3,0.4,0.5,0.7 or 0.9 etc., the value of z can for 0,0.1,
0.2,0.3,0.4,0.5,0.7 or 0.9 etc., i.e., the described metallic element M can contain or not contain, and the M is typical but non-
Restrictive combination such as Li and Mg, Zn and Ni, Li, Mg and Zn etc..The preset ratio can be any ratio.
The metal M in Li, Mg, Zn or Ni any one or at least two combination.
Preparation method provided by the invention uses ammonium hydroxide for chelating agent, and sodium hydroxide is coprecipitator, using coprecipitation
It is prepared for Cu-Fe-Mn layered oxide presoma, and adjusting process condition, the Cu-Fe-Mn layer of different-shape can be obtained
Shape oxide precursor, the Cu-Fe-Mn layered oxide presoma are used to prepare sodium-ion battery positive electrode with excellent
Chemical property.
Step (1) copper source is selected from mantoquita, appointing preferably in the nitrate of the sulfate of copper, the chloride of copper or copper
It anticipates a kind of or at least two combinations, typical but non-limiting combination such as the sulfate of copper and the chloride of copper, the sulfuric acid of copper
The nitrate of salt and copper, the nitrate of the sulfate of copper, the chloride of copper and copper.The sulfate of the copper is preferably copper sulphate,
The chloride of the copper is preferably copper chloride, and the nitrate of the copper is preferably copper nitrate.
Preferably, step (1) source of iron is selected from molysite, the preferably nitric acid of the sulfate of iron, the chloride of iron or iron
In salt any one or at least two combination, typical but non-limiting combination such as the sulfate of iron and the chloride of iron,
The sulfate of iron and the nitrate of iron, the nitrate of the sulfate of iron, the chloride of iron and iron.The sulfate of the iron is preferably
Ferric sulfate and/or ferrous sulfate, the chloride of the iron are preferably iron chloride and/or frerrous chloride, and the nitrate of the iron is excellent
It is selected as ferric nitrate and/or ferrous nitrate.
Preferably, step (1) manganese source is selected from manganese salt, the preferably nitric acid of the sulfate of manganese, the chloride of manganese or manganese
In salt any one or at least two combination, typical but non-limiting combination such as the sulfate of manganese and the chloride of manganese,
The sulfate of manganese and the nitrate of manganese, the nitrate of the sulfate of manganese, the chloride of manganese and manganese.The sulfate of the manganese is preferably
Manganese sulfate, the chloride of the manganese are preferably manganese chloride, and the nitrate of the manganese is preferably manganese nitrate.
Preferably, step (1) source the metal M is selected from metal M salt, the preferably chlorination of the sulfate of metal M, metal M
In the nitrate of object or metal M any one or at least two combination, it is typical but non-limiting combination as M sulfate
With the chloride of M, the sulfate of M and the nitrate of M, the nitrate of the sulfate of M, the chloride of M and M.
In step (1) acquired solution the total concentration of metal ion be 0.5-2.5M, i.e. 0.5-2.5mol/L, as 0.6M,
0.8M, 0.9M, 1.0M, 1.2M, 1.5M or 2.2M etc..Copper source, source of iron, manganese source and the molar ratio in the source M can be used pre-
If arbitrary proportion, as long as the total concentration of its metal ion be 0.5-2.5M.
Step (2) protective atmosphere is selected from nitrogen atmosphere and/or inert gas atmosphere.
Preferably, the concentration of step (2) described sodium hydroxide solution be 1-5M, i.e. 1-5mol/L, as 1.5mol/L,
2.2mol/L, 2.8mol/L, 3.4mol/L, 3.8mol/L, 4.3mol/L or 4.8mol/L etc..
Preferably, the mole of sodium hydroxide is that metal ion rubs in mixed liquor in step (2) described sodium hydroxide solution
2.0-5.8 times of that amount, such as 2.5 times, 3.0 times, 3.5 times, 3.8 times, 4.2 times, 4.5 times, 5.2 times or 5.5 times.Sodium hydroxide
Additional amount very few to will lead to precipitating incomplete.
Preferably, the concentration of step (2) described ammonium hydroxide be 5wt%-50wt%, as 6wt%, 8wt%, 10wt%,
12wt%, 15wt%, 18wt%, 20wt%, 25wt%, 30wt%, 35wt%, 38wt%, 42wt% or 48wt% etc., it is described
Ammonium hydroxide plays complexing in preparation method, is easy to regulate and control the pattern of product, and ammonium hydroxide content cannot be excessively high, otherwise Cu easily with
Ammonium hydroxide forms complex compound, causes Cu precipitating incomplete；Ammonium hydroxide content can not be too low, does not otherwise have the effect of complexing regulation,
The concentration of ammonium hydroxide is preferably 5-50wt%.
Preferably, the molar ratio of copper ion is 1-8:1 in the ammonia and mixed liquor in step (2) described ammonium hydroxide, such as 1.5,
2.0,2.3,2.8,3.2,3.5,4.0,4.3,4.5,4.9,5.3,5.8,6.0,6.8 or 7.5 etc..
Preferably, mixed form described in step (2) is to be added dropwise.
Preferably, step (2) rate of addition is constant speed, the i.e. drop of mixed liquor, sodium hydroxide solution and ammonium hydroxide three
Acceleration is preferably that constant speed is added dropwise.
Preferably, step (2) mixed liquor, sodium hydroxide solution and ammonium hydroxide are independently dripped with the mobility of 1-5mL/min
Mixing in reactor is added to be reacted.The rate of addition of the mixed liquor, sodium hydroxide solution and ammonium hydroxide all can be 1-
Arbitrary value between 5mL/min, as 1.2mL/min, 1.8mL/min, 2.3mL/min, 2.8mL/min, 3.4mL/min,
The rate of addition of 3.6mL/min, 4.3mL/min or 4.6mL/min etc., three can be identical also not identical.I.e. step (2) is described
Mixed liquor, sodium hydroxide solution and ammonium hydroxide are independently added dropwise to mixing in reactor with the constant current degree of 1-5mL/min and are reacted.
Preferably, step (2) mixing carries out under agitation, and the speed of stirring is preferably 800rpm or more, such as
850rpm, 900rpm, 950rpm, 1000rpm, 1500rpm, 2000rpm or 3000rpm etc..Further preferably 800-
2500rpm。
Preferably, it is described stir use agitating paddle arm exhibition be 2-9.5cm, as 2.5cm, 3.0cm, 4.0cm, 5.0cm,
6.0cm, 7.0cm or 8.5cm etc..
The temperature of step (2) described reaction be 40-80 DEG C, such as 42 DEG C, 45 DEG C, 48 DEG C, 50 DEG C, 53 DEG C, 58 DEG C, 60 DEG C,
65 DEG C, 72 DEG C or 76 DEG C etc..
Preferably, the time of step (2) described reaction is 1-7h, such as 2h, 3h, 4h, 5h, 6h or 6.5h.
Step (3) post-processing includes curing, cooling, is separated by solid-liquid separation, washing and drying.
Preferably, the time of the curing is 0.5-2h, such as 0.8h, 1.0h, 1.3h, 1.8h or 1.9h.
Preferably, it is cooled to natural cooling.
Preferably, the washing includes washing, until water lotion is neutrality.
The preparation method of the Cu-Fe-Mn layered oxide presoma includes following step as a preferred technical solution,
It is rapid:
(1) copper source, source of iron and manganese source are prepared into mixed liquor according to preset ratio；Or, by copper source, source of iron and manganese source and gold
Belong to the source M and is prepared into mixed liquor according to preset ratio；The total concentration of metal ion is 0.5-2.5M in mixed liquor；
(2) in protective atmosphere and under conditions of mixing speed is 800-1200rpm, by mixed liquor, concentration 1-5M
Sodium hydroxide solution and concentration be 5-50wt% ammonium hydroxide independently with the constant current degree of 1-5mL/min be added dropwise in reactor mix
Conjunction is reacted, and the temperature of reaction is 40-80 DEG C, and the time of reaction is 1-7h, obtains reaction product, wherein the ammonia in ammonium hydroxide
Molar ratio with copper ion in mixed liquor is 1-8；In sodium hydroxide solution the mole of sodium hydroxide be mixed liquor in metal from
2.0-5.8 times of sub- mole；
(3) reaction product obtained by step (2) is cured into 0.5-2h, later natural cooling, is separated by solid-liquid separation, is washed to water lotion
For neutrality, drying obtains Cu-Fe-Mn layered oxide presoma.
Preferably, the ratio between mole of metal ion integral molar quantity and ammonium hydroxide is 0.2- in step (2) described mixed liquor
1.3, such as 0.3,0.5,0.7,0.8,1.0,1.2 or 1.3, mixing speed 800-25000rpm, as 1000rpm,
1500rpm, 3000rpm, 5000rpm, 8000rpm, 12000rpm, 15000rpm or 22000rpm etc., the arm of agitating paddle used
Exhibition is 2-8cm, such as when 3cm, 4cm, 5cm, 6cm or 7cm, obtains tubulose Cu-Fe-Mn layered oxide presoma.
Preferably, the ratio between mole of metal ion integral molar quantity and ammonium hydroxide is 1.4-8 in step (2) described mixed liquor,
Such as 1.5,1.8,2.3,2.5,2.8,3.5,3.8,4.0,5.0,6.0,7.0 or 7.8, mixing speed 800-2500rpm, such as
1000rpm, 1500rpm, 3000rpm, 5000rpm, 8000rpm, 12000rpm, 15000rpm or 22000rpm etc., it is used to stir
The arm exhibition for mixing paddle is 2-6cm, such as when 3cm, 4cm, 5cm or 5.5cm, obtains the graininess Cu-Fe-Mn stratiform oxygen of uniform accumulation
Compound presoma.
Preferably, the ratio between mole of metal ion integral molar quantity and ammonium hydroxide is 1.4-8 in step (2) described mixed liquor,
Such as 1.5,1.8,2.3,2.5,2.8,3.5,3.8,4.0,5.0,6.0,7.0 or 7.8, mixing speed 800-2500rpm, such as
1000rpm, 1500rpm, 3000rpm, 5000rpm, 8000rpm, 12000rpm, 15000rpm or 22000rpm etc., it is used to stir
Mixing paddle arm exhibition is 6.2-9.5cm, such as when 6.5cm, 6.8cm, 7.5cm, 8.0cm, 8.5cm or 9.0cm, obtains microspheroidal Cu-
Fe-Mn layered oxide presoma.The arm exhibition of the agitating paddle refers to the length after the expansion of double leaf agitating paddle blade, i.e. two paddles
The sum of length of leaf.
The production of the available different-shape of preparation method of Cu-Fe-Mn layered oxide presoma i.e. provided by the invention
Object.
The second object of the present invention is to provide a kind of Cu-Fe-Mn layered oxide that preparation method as described above obtains
Presoma.
The third object of the present invention is to provide the purposes of Cu-Fe-Mn layered oxide presoma described in one kind, uses
In preparation Cu-Fe-Mn sodium salt layered oxide, and then it is used to prepare sodium-ion battery positive material.
Specifically, using the side of the Cu-Fe-Mn layered oxide precursor preparation Cu-Fe-Mn sodium salt layered oxide
Method includes: to mix Cu-Fe-Mn layered oxide presoma with sodium carbonate according to stoichiometry, grinding, in 800-1000
10-24h is calcined under the conditions of DEG C, obtains Cu-Fe-Mn sodium salt layered oxide.The temperature of the calcining can for 820 DEG C, 850 DEG C,
880 DEG C, 890 DEG C, 920 DEG C, 950 DEG C, 940 DEG C, 960 DEG C or 980 DEG C etc., time of the calcining can for 12h, 14h, 18h,
20h or 22h etc..
Numberical range of the present invention not only includes enumerated point value, further includes the above-mentioned numerical value not included
Arbitrary point value between range, as space is limited and for concise consideration, range described in the present invention no longer exclusive list includes
Specific point value.
Compared with prior art, the invention has the benefit that
Sodium-ion battery provided by the invention is simple with the preparation method of Cu-Fe-Mn layered oxide presoma, is easy to grasp
Make, process conditions mutually cooperate with, and can be prepared by the uniform Cu-Fe-Mn layered oxide of each distributions of metallic elements by co-precipitation
Presoma, at low cost, less energy consumption, and Cu-Fe-Mn layered oxide presoma close to spherical shape can be obtained；
Cu- made from preparation method of the sodium-ion battery provided by the invention with Cu-Fe-Mn layered oxide presoma
The Cu-Fe-Mn sodium salt stratiform that electrochemical performance can be obtained through conventional treatment in Fe-Mn layered oxide presoma aoxidizes
Object；The all specific discharge capacities of head of product are obtained up to 90.0mAh/g.Under the current ratio of low range 0.1C, by 5 weeks follow
After ring, the specific discharge capacity with 89.1mAh/g, capacity retention ratio is up to 98.54%.
The preparation method of sodium-ion battery provided by the invention Cu-Fe-Mn layered oxide presoma convenient for promote and
Industrialization.
Detailed description of the invention
Fig. 1 is the SEM figure for the Cu-Fe-Mn layered oxide presoma that embodiment 1 obtains.
Fig. 2 is the SEM figure for the Cu-Fe-Mn layered oxide presoma that embodiment 2 obtains.
Fig. 3 is the SEM figure for the Cu-Fe-Mn layered oxide presoma that embodiment 3 obtains.
Fig. 4 is the SEM figure for the Cu-Fe-Mn layered oxide presoma that embodiment 4 obtains.
Fig. 5 is the SEM figure for the Cu-Fe-Mn layered oxide presoma that embodiment 5 obtains.
Fig. 6 is the charging and discharging curve figure that embodiment 4 provides.
Fig. 7 is the XRD diagram that embodiment 4 provides.
Fig. 8 is the corresponding SEM-EDS mapping of embodiment 4 figure, wherein (a) is EDS layered image；It (b) is Cu element
Distribution map；It (c) is Fe distribution diagram of element；It (d) is Mn distribution diagram of element.
Specific embodiment
To further illustrate the technical scheme of the present invention below with reference to the accompanying drawings and specific embodiments.
Embodiment 1
A kind of Cu-Fe-Mn layered oxide presoma (composition are as follows: Cu1/3Fe1/3Mn1/3(OH)2) preparation method, including
Following steps:
(1) copper sulphate, ferrous sulfate and manganese sulfate are prepared into according to Cu:Fe:Mn molar ratio=1:1:1 mixed dissolution
Mixed liquor, the total concentration of metal ion is 1.5M in mixed liquor；
(2) in nitrogen atmosphere, mixing speed is 1000rpm and the exhibition of the arm of agitating paddle is under conditions of be 6cm, 20mL is mixed
Liquid, the sodium hydroxide solution that 22mL concentration is 3M and the ammonium hydroxide that 22mL concentration is 1.9M are closed independently with the constant current of 1.2mL/min
Degree is added dropwise to mixing in reactor and is reacted, and the temperature of reaction is 60 DEG C, and the time of reaction is 1h, obtains reaction product；
(3) reaction product obtained by step (2) is cured into 1h, later natural cooling, be separated by solid-liquid separation, is washed to during water lotion is
Property, drying obtains Cu-Fe-Mn layered oxide presoma.
Embodiment 2
A kind of Cu-Fe-Mn layered oxide presoma (composition are as follows: Cu0.2Fe0.3Mn0.5(OH)2) preparation method, including
Following steps:
(1) copper sulphate, ferrous sulfate and manganese sulfate are prepared into according to Cu:Fe:Mn molar ratio=2:3:5 mixed dissolution
Mixed liquor, the total concentration of metal ion is 1.5M in mixed liquor；
(2) in nitrogen atmosphere, mixing speed is 1000rpm and the exhibition of the arm of agitating paddle is under conditions of be 5cm, by 250mL
The ammonium hydroxide that the sodium hydroxide solution and 250mL concentration that mixed liquor, 275mL concentration are 3M are 1.0M is independently with 1.2mL/min's
Constant current degree is added dropwise to mixing in reactor and is reacted, and the temperature of reaction is 55 DEG C, and the time of reaction is 6h, obtains reaction and produces
Object；
(3) reaction product obtained by step (2) is cured into 1h, later natural cooling, be separated by solid-liquid separation, is washed to during water lotion is
Property, drying obtains Cu-Fe-Mn layered oxide presoma.
A kind of Cu-Fe-Mn layered oxide presoma (composition are as follows: Cu0.2Fe0.3Mn0.5(OH)2) preparation method, including
Following steps:
(1) copper sulphate, ferrous sulfate and manganese sulfate are prepared into according to Cu:Fe:Mn molar ratio=2:3:5 mixed dissolution
Mixed liquor, the total concentration of metal ion is 2.5M in mixed liquor；
(2) in nitrogen atmosphere, mixing speed is 1000rpm and the exhibition of the arm of agitating paddle is under conditions of be 8.5cm, will
The ammonium hydroxide that the sodium hydroxide solution and 250mL concentration that 250mL mixed liquor, 275mL concentration are 5M are 1.50M is independently with 1.2mL/
The constant current degree of min is added dropwise to mixing in reactor and is reacted, and the temperature of reaction is 55 DEG C, and the time of reaction is 6h, obtains anti-
Answer product；
(3) reaction product obtained by step (2) is cured into 1h, later natural cooling, be separated by solid-liquid separation, is washed to during water lotion is
Property, drying obtains Cu-Fe-Mn layered oxide presoma.
A kind of Cu-Fe-Mn layered oxide presoma (composition are as follows: Cu0.2Fe0.3Mn0.5(OH)2) preparation method, including
Following steps:
(1) copper sulphate, ferrous sulfate and manganese sulfate are prepared into according to Cu:Fe:Mn molar ratio=2:3:5 mixed dissolution
Mixed liquor, the total concentration of metal ion is 2.5M in mixed liquor；
(2) in nitrogen atmosphere, mixing speed is 2500rpm and the exhibition of the arm of agitating paddle is under conditions of be 7.0cm, will
The ammonium hydroxide that the sodium hydroxide solution and 250mL concentration that 250mL mixed liquor, 275mL concentration are 5M are 1.70M is independently with 1.2mL/
The constant current degree of min is added dropwise to mixing in reactor and is reacted, and the temperature of reaction is 55 DEG C, and the time of reaction is 6h, obtains anti-
Answer product；
(3) reaction product obtained by step (2) is cured into 1h, later natural cooling, be separated by solid-liquid separation, is washed to during water lotion is
Property, drying obtains Cu-Fe-Mn layered oxide presoma.
Embodiment 5
A kind of Cu-Fe-Mn layered oxide presoma (composition are as follows: Cu1/12Fe1/3Mn1/3Ni1/4(OH)2) preparation method,
Include the following steps:
(1) copper sulphate, ferrous sulfate, manganese sulfate and nickel sulfate are mixed according to Cu:Fe:Mn:Ni molar ratio=1:4:4:3
Dissolution is prepared into mixed liquor, and the total concentration of metal ion is 2.5M in mixed liquor；
(2) in nitrogen atmosphere, mixing speed is 2500rpm and the exhibition of the arm of agitating paddle is under conditions of be 4cm, by 250mL
The ammonium hydroxide that the sodium hydroxide solution and 250mL concentration that mixed liquor, 275mL concentration are 5M are 1.70M is independently with 1.2mL/min's
Constant current degree is added dropwise to mixing in reactor and is reacted, and the temperature of reaction is 55 DEG C, and the time of reaction is 6h, obtains reaction and produces
Object；
(3) reaction product obtained by step (2) is cured into 1h, later natural cooling, be separated by solid-liquid separation, is washed to during water lotion is
Property, drying obtains Cu-Fe-Mn layered oxide presoma.
SEM test is carried out to the product that embodiment 1-5 is obtained, test result difference is as shown in Figs. 1-5, can from figure
Out, the presoma of uniform morphology can be obtained under the experiment condition of setting: the product morphology that embodiment 1 obtains is as shown in Figure 1
For tubulose；The product morphology that embodiment 2 obtains is illustrated in figure 2 the particle of uniform accumulation；The product morphology that embodiment 3 obtains is such as
Fig. 3 show micro-sphere structure；The product morphology that embodiment 4 obtains is illustrated in figure 4 microballoon；The product morphology that embodiment 5 obtains
It is illustrated in figure 5 the particle of uniform accumulation.
Wherein, the nickel sulfate in embodiment 5 replace in lithium source, magnesium source or zinc source any one or at least two group
It closes, can equally obtain layered oxide presoma.The lithium source, magnesium source or zinc source can be its sulfate, chloride or nitre
In hydrochlorate any one or at least two combination.
In addition, through testing, by metal ion integral molar quantity and ammonium hydroxide rub in step (2) described mixed liquor in embodiment 1
The ratio between your amount is adjusted to 0.2-1.4, such as 0.3,0.5,0.7,0.8,1.0,1.2 or 1.3, and mixing speed is adjusted to 800-
25000rpm, such as 1000rpm, 1500rpm, 3000rpm, 5000rpm, 8000rpm, 12000rpm, 15000rpm or
The arm exhibition of 22000rpm etc., agitating paddle used are adjusted to 2-8cm, such as when 3cm, 4cm, 5cm, 6cm or 7cm, can obtain pipe
Shape Cu-Fe-Mn layered oxide presoma.
Through testing, by metal ion integral molar quantity and ammonium hydroxide in step (2) described mixed liquor in embodiment 2 or embodiment 5
The ratio between mole be adjusted to 1.4-8, such as 1.5,1.8,2.3,2.5,2.8,3.5,3.8,4.0,5.0,6.0,7.0 or 7.8,
Mixing speed is adjusted to 800-2500rpm, as 1000rpm, 1500rpm, 3000rpm, 5000rpm, 8000rpm, 12000rpm,
The arm exhibition of 15000rpm or 22000rpm etc., agitating paddle used are adjusted to 2-6cm, such as when 3cm, 4cm, 5cm or 5.5cm,
The graininess Cu-Fe-Mn layered oxide presoma of available uniform accumulation.
Through testing, by metal ion integral molar quantity and ammonium hydroxide in step (2) described mixed liquor in embodiment 3 or embodiment 4
The ratio between mole be adjusted to 1.4-8, such as 1.5,1.8,2.3,2.5,2.8,3.5,3.8,4.0,5.0,6.0,7.0 or 7.8,
Mixing speed is adjusted to 800-2500rpm, as 1000rpm, 1500rpm, 3000rpm, 5000rpm, 8000rpm, 12000rpm,
15000rpm or 22000rpm etc., stirring paddle arm used exhibition are adjusted to 6.2-9.5cm, as 6.5cm, 6.8cm, 7.5cm, 8.0cm,
Whens 8.5cm or 9.0cm etc., microspheroidal Cu-Fe-Mn layered oxide presoma can be obtained.
The production of the available different-shape of preparation method of Cu-Fe-Mn layered oxide presoma i.e. provided by the invention
Object.
Embodiment 6
A kind of sodium-ion battery preparation method of Cu-Fe-Mn sodium salt layered oxide, includes the following steps:
According to the metering ratio of reaction, 4 gained Cu-Fe-Mn layered oxide presoma of embodiment is mixed with sodium carbonate and is ground
Mill, calcine 12h under the conditions of 900 DEG C, obtain Cu-Fe-Mn sodium salt layered oxide (composition are as follows:
Na0.9Cu0.22Fe0.3Mn0.48O2).Electrochemical property test is carried out to it, it is as a result as shown in fig. 6, it can be seen from the figure that spherical
The first all discharge capacities of the battery material that presoma obtains after the sintering are 90.1mAh/g, and after 7 weeks recycle, capacity still may be used
It is maintained at 89.1mAh/g.
Embodiment 7
A kind of Cu-Fe-Mn layered oxide presoma (composition are as follows: Cu0.2Fe0.3Mn0.5(OH)2) preparation method, including
Following steps:
(1) copper sulphate, ferrous sulfate and manganese sulfate are prepared into according to Cu:Fe:Mn molar ratio=2:3:5 mixed dissolution
Mixed liquor, the total concentration of metal ion is 0.5M in mixed liquor；
(2) in nitrogen atmosphere and under conditions of mixing speed is 2500rpm, by mixed liquor, the hydroxide that concentration is 1M
The ammonium hydroxide that sodium solution and concentration are 5wt% is independently added dropwise to mixing in reactor with the constant current degree of 1.0mL/min and is reacted,
The temperature of reaction is 40 DEG C, and the time of reaction is 7h, obtains reaction product；Mole of copper ion in ammonia and mixed liquor in ammonium hydroxide
Than being 1；The mole of sodium hydroxide is 2.0 times of metal ion mole in mixed liquor in sodium hydroxide solution；
(3) reaction product obtained by step (2) is cured into 0.5h, later natural cooling, be separated by solid-liquid separation, being washed to water lotion is
Neutrality, drying, obtains Cu-Fe-Mn layered oxide presoma.
Embodiment 8
A kind of Cu-Fe-Mn layered oxide presoma (composition are as follows: Cu0.2Fe0.3Mn0.5(OH)2) preparation method, including
Following steps:
(1) copper sulphate, ferrous sulfate and manganese sulfate are prepared into according to Cu:Fe:Mn molar ratio=2:3:5 mixed dissolution
Mixed liquor, the total concentration of metal ion is 2.5M in mixed liquor；
(2) under conditions of being in an inert gas atmosphere 800rpm with mixing speed, the hydrogen for the 5M for being by mixed liquor, concentration
The ammonium hydroxide that sodium hydroxide solution and concentration are 50wt% independently is added dropwise to mix in reactor with the constant current degree of 5.0mL/min and be carried out
Reaction, the temperature of reaction are 80 DEG C, and the time of reaction is 1h, obtain reaction product；Copper ion in ammonia and mixed liquor in ammonium hydroxide
Molar ratio be 8；The mole of sodium hydroxide is 5.8 times of metal ion mole in mixed liquor in sodium hydroxide solution；
(3) reaction product obtained by step (2) is cured into 2h, later natural cooling, be separated by solid-liquid separation, is washed to during water lotion is
Property, drying obtains Cu-Fe-Mn layered oxide presoma.
Embodiment 9
A kind of Cu-Fe-Mn layered oxide presoma (composition are as follows: Cu0.2Fe0.3Mn0.5(OH)2) preparation method, including
Following steps:
(1) copper sulphate, ferrous sulfate and manganese sulfate are prepared into according to Cu:Fe:Mn molar ratio=2:3:5 mixed dissolution
Mixed liquor, the total concentration of metal ion is 2.5M in mixed liquor；
(2) under conditions of being in an inert gas atmosphere 1500rpm with mixing speed, the 2M that is by mixed liquor, concentration
The ammonium hydroxide that sodium hydroxide solution and concentration are 20wt%, which is independently added dropwise in reactor with the constant current degree of 3.0mL/min, to be mixed into
Row reaction, the temperature of reaction are 50 DEG C, and the time of reaction is 5h, obtain reaction product；In ammonia and mixed liquor in ammonium hydroxide copper from
The molar ratio of son is 5；The mole of sodium hydroxide is 4.0 times of metal ion mole in mixed liquor in sodium hydroxide solution；
(3) reaction product obtained by step (2) is cured into 1h, later natural cooling, be separated by solid-liquid separation, is washed to during water lotion is
Property, drying obtains Cu-Fe-Mn layered oxide presoma.
The residual concentration of each metal ion in the filtrate in embodiment 1-5 and 7-9 in step (3) is detected, as a result such as table 1
It is shown:
Table 1
As it can be seen from table 1 each embodiment shows that tenor is all in 1.5ppm hereinafter, say in the filtrate of washed product
Bright metal realizes precipitating completely, achievees the effect that co-precipitation.
XRD test is carried out after the presoma sintering that embodiment 1-5,7-9 is obtained, wherein the test result knot of embodiment 4
Fruit is as shown in fig. 7, it can be seen from the figure that the XRD for obtaining sintered product is shown as pure phase structure, and crystallinity is good.It is other
Embodiment can equally prepare the sintered product of default composition, and XRD result is also shown as pure phase structure, and crystallinity is good
It is good.
The presoma that embodiment 1-5,7-9 is obtained carries out SEM-EDS mapping test, the wherein test of embodiment 4
Result is as shown in figure 8, as can be seen from the figure the correspondence of three kinds of elements and material of main part is good, in provable product respectively
Elemental redistribution is uniform.Each element is also to be uniformly distributed in the presoma that other embodiments obtain.
The obtained presoma of embodiment 1-3,5,7-9 is prepared as follows into positive electrode:
According to stoichiometry, above-mentioned layered oxide presoma is mixed with sodium carbonate, is ground, at 800-1000 DEG C
10-24h (such as 12h or 20h) is calcined under the conditions of (such as 850 DEG C or 950 DEG C), obtains Cu-Fe-Mn sodium salt layered oxide.
Gained Cu-Fe-Mn sodium salt layered oxide is prepared into positive electrode, and tests its chemical property.Its chemical property knot
Fruit shows that the first all discharge capacities of battery material obtained are up to 90-110mAh/g, recycles through 100 weeks, capacity retention ratio exists
92%-96%.
Comparative example 1
A kind of preparation method of Cu-Fe-Mn layered oxide presoma, except step (2) replace with sodium hydroxide solution
Outside sodium carbonate liquor, remaining is same as Example 1.
Obtained Cu-Fe-Mn layered oxide presoma is prepared into positive electrode according to method described in embodiment 6,
Electrochemical property test is carried out to it, the results show that the first all discharge capacities of battery material obtained were 79.2mAh/g, through 100 weeks
Circulation, capacity retention ratio only have 69.3%.
Comparative example 2
A kind of preparation method of Cu-Fe-Mn layered oxide presoma, except ammonium hydroxide is replaced with urea liquid by step (2)
Outside, remaining is same as Example 1.
Obtained Cu-Fe-Mn layered oxide presoma is prepared into positive electrode according to method described in embodiment 6,
Electrochemical property test is carried out to it, the results show that the first all discharge capacities of battery material obtained were 68.3mAh/g, through 100 weeks
Circulation, capacity retention ratio only 72.5%.
The Applicant declares that the foregoing is merely a specific embodiment of the invention, but protection scope of the present invention not office
It is limited to this, it should be clear to those skilled in the art, any to belong to those skilled in the art and take off in the present invention
In the technical scope of dew, any changes or substitutions that can be easily thought of, and all of which fall within the scope of protection and disclosure of the present invention.
Claims (20)
1. a kind of method using Cu-Fe-Mn layered oxide precursor preparation Cu-Fe-Mn sodium salt layered oxide, described
The chemical general formula of Cu-Fe-Mn layered oxide presoma is CuxFeyMzMn1-x-y-z(OH)2, wherein 0 < x < 1,0 < y < 1,0≤z <
1, wherein M is metallic element, which is characterized in that the preparation method of the Cu-Fe-Mn layered oxide presoma includes following step
It is rapid:
(1) copper source, source of iron and manganese source are prepared into mixed liquor according to preset ratio；Or, by copper source, source of iron and manganese source and metal M
Source is prepared into mixed liquor according to preset ratio；
(2) in protective atmosphere, mixed liquor, sodium hydroxide solution and ammonium hydroxide are mixed and is reacted, the hydrogen-oxygen simultaneously
The mole for changing sodium hydroxide in sodium solution is ammonia 2.0-5.8 times of metal ion mole in mixed liquor, in ammonium hydroxide and mix
The molar ratio for closing copper ion in liquid is 1-8:1, obtains reaction product；The concentration of the ammonium hydroxide is 5wt%-50wt%, described
Mixed form is to be added dropwise, and the rate of addition is constant speed, and the mixed liquor, sodium hydroxide solution and ammonium hydroxide are independently with 1-5mL/
The mobility of min is added dropwise to mixing in reactor and is reacted；The mixing carries out under agitation, and the speed of the stirring is
800rpm or more, the arm exhibition for stirring the agitating paddle used is 2-9.5cm；The temperature of the reaction is 40-80 DEG C；
(3) reaction product obtained by step (2) is post-processed, obtains Cu-Fe-Mn layered oxide presoma, the presoma
Pattern is the combination of any one or at least two in tubulose, graininess and microspheroidal；Metal ion is total in the mixed liquor
The ratio between mole and the mole of ammonium hydroxide are 0.2-1.3, the exhibition of the arm of mixing speed 800-25000rpm, agitating paddle used is 2-
When 8cm, tubulose Cu-Fe-Mn layered oxide presoma is obtained；Metal ion integral molar quantity and ammonium hydroxide rubs in the mixed liquor
The ratio between your amount be 1.4-8, the arm of mixing speed 800-2500rpm, agitating paddle used is opened up when being 2-6cm, obtained graininess
Cu-Fe-Mn layered oxide presoma；The ratio between mole of metal ion integral molar quantity and ammonium hydroxide is 1.4- in the mixed liquor
8, when mixing speed 800-2500rpm, stirring paddle arm used exhibition are 6.2-9.5cm, microspheroidal Cu-Fe-Mn stratiform oxygen is obtained
Compound presoma；
Method using the Cu-Fe-Mn layered oxide precursor preparation Cu-Fe-Mn sodium salt layered oxide include: according to
Stoichiometry mixes Cu-Fe-Mn layered oxide presoma with sodium carbonate, and grinding is calcined under the conditions of 800-1000 DEG C
10-24h obtains Cu-Fe-Mn sodium salt layered oxide；
The all specific discharge capacities of head of product are obtained up to 90.0mAh/g；Under the current ratio of low range 0.1C, by 5 weeks
After circulation, the specific discharge capacity with 89.1mAh/g, capacity retention ratio is up to 98.54%.
2. the method according to claim 1, wherein step (1) copper source is selected from mantoquita.
3. according to the method described in claim 2, it is characterized in that, step (1) copper source is the chlorination of the sulfate, copper of copper
In the nitrate of object or copper any one or at least two combination.
4. the method according to claim 1, wherein step (1) source of iron is selected from molysite.
5. according to the method described in claim 4, it is characterized in that, step (1) source of iron is the chlorination of the sulfate, iron of iron
In the nitrate of object or iron any one or at least two combination.
6. the method according to claim 1, wherein step (1) manganese source is selected from manganese salt.
7. according to the method described in claim 6, it is characterized in that, step (1) manganese source is the chlorination of the sulfate, manganese of manganese
In the nitrate of object or manganese any one or at least two combination.
8. the method according to claim 1, wherein the metal M is any one in Li, Mg, Zn or Ni
Kind or at least two combination.
9. the method according to claim 1, wherein step (1) source the metal M is selected from metal M salt.
10. the method according to claim 1, wherein step (1) source the metal M be metal M sulfate,
In the chloride of metal M or the nitrate of metal M any one or at least two combination.
11. the method according to claim 1, wherein the total concentration of metal ion is in step (1) acquired solution
0.5-2.5M。
12. the method according to claim 1, wherein step (2) protective atmosphere is selected from nitrogen atmosphere
And/or inert gas atmosphere.
13. the method according to claim 1, wherein the concentration of step (2) described sodium hydroxide solution is 1-
5M。
14. the method according to claim 1, wherein the speed of the stirring is 800-2500rpm.
15. the method according to claim 1, wherein the time of step (2) described reaction is 1-7h.
16. the method according to claim 1, wherein step (3) post-processing includes curing, cooling, solid-liquid
Separation, washing and drying.
17. according to the method for claim 16, which is characterized in that the time of the curing is 0.5-2h.
18. according to the method for claim 16, which is characterized in that described to be cooled to natural cooling.
19. according to the method for claim 16, which is characterized in that the washing includes washing, until water lotion is neutrality.
20. the method according to claim 1, wherein the preparation method includes the following steps:
(1) copper source, source of iron and manganese source are prepared into mixed liquor according to preset ratio；Or, by copper source, source of iron and manganese source and metal M
Source is prepared into mixed liquor according to preset ratio；The total concentration of metal ion is 0.5-2.5M in mixed liquor；
(2) in protective atmosphere and under conditions of mixing speed is 800-2500rpm, by mixed liquor, the hydrogen that concentration is 1-5M
The ammonium hydroxide that sodium hydroxide solution and concentration are 5-50wt%, which is independently added dropwise in reactor with the constant current degree of 1-5mL/min, to be mixed into
Row reaction, the temperature of reaction are 40-80 DEG C, and the time of reaction is 1-7h, obtain reaction product, wherein ammonium hydroxide and step (1) institute
The molar ratio for obtaining copper ion in solution is 1-8；The mole of sodium hydroxide is metal ion in mixed liquor in sodium hydroxide solution
2.0-5.8 times of mole；
(3) reaction product obtained by step (2) is cured into 0.5-2h, later natural cooling, be separated by solid-liquid separation, is washed to during water lotion is
Property, drying obtains Cu-Fe-Mn layered oxide presoma.
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| CN110947395A (en) * | 2019-12-03 | 2020-04-03 | 中化环境控股有限公司 | Preparation method of Fenton-like catalytic material and sewage treatment method |
| CN113666424B (en) * | 2021-09-29 | 2023-07-14 | 南通金通储能动力新材料有限公司 | Precursor of sodium ion battery anode material and preparation method thereof |
| CN114050257B (en) * | 2021-11-12 | 2023-02-24 | 蜂巢能源科技有限公司 | Manganese-iron-copper positive electrode precursor material and preparation method and application thereof |
| CN114835173B (en) * | 2022-04-21 | 2024-07-19 | 蜂巢能源科技股份有限公司 | Positive electrode material precursor, preparation method thereof and positive electrode material |
| CN114988481B (en) * | 2022-04-28 | 2023-10-13 | 南通金通储能动力新材料有限公司 | Sodium ion battery anode material precursor and preparation method thereof |
| CN114853071B (en) * | 2022-05-12 | 2023-10-13 | 南通金通储能动力新材料有限公司 | Sodium ion positive electrode material precursor with multilayer structure and preparation method thereof |
| CN114956211B (en) * | 2022-08-02 | 2022-10-25 | 蜂巢能源科技股份有限公司 | Manganese-nickel-copper precursor, sodium ion battery positive electrode material and preparation method thereof |
| CN115611319B (en) * | 2022-09-22 | 2023-10-24 | 湖南工程学院 | Copper-iron-manganese-based positive electrode material of sodium ion battery and preparation method thereof |
| CN116081707A (en) * | 2022-12-22 | 2023-05-09 | 北京当升材料科技股份有限公司 | Positive electrode material precursor and preparation method thereof, positive electrode material for sodium ion battery and preparation method thereof, and sodium ion battery |
| CN116081708A (en) * | 2022-12-27 | 2023-05-09 | 华南师范大学 | Layered material, preparation method thereof, positive electrode material and sodium ion battery |
| CN115966687A (en) * | 2023-02-24 | 2023-04-14 | 荆门市格林美新材料有限公司 | Layered sodium-ion battery positive electrode material and preparation method and application thereof |
| CN116443955B (en) * | 2023-06-14 | 2023-09-26 | 宜宾光原锂电材料有限公司 | Nickel-iron-copper-manganese precursor, preparation method thereof, positive electrode material and battery |
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