CN109638274A - A kind of molybdenum ytterbium is co-doped with silicic acid ferrisodium combination electrode material and preparation method thereof - Google Patents
A kind of molybdenum ytterbium is co-doped with silicic acid ferrisodium combination electrode material and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to a kind of molybdenum ytterbiums to be co-doped with silicic acid ferrisodium combination electrode material and its preparation method and application, and the molecular formula of the combination electrode material is Na2‑x‑yFeMoxYbySiO4/ C, wherein 0 < x≤0.2,0 < y≤0.2.The present invention is modified silicic acid ferrisodium using molybdenum and ytterbium co-doped, it is compound that highly conductive carbon source progress is introduced simultaneously, the chemical property of silicic acid ferrisodium is effectively improved, the molybdenum ytterbium with high conductivity, height ratio capacity, high-rate characteristics and long circulation life has been obtained and has been co-doped with silicic acid ferrisodium combination electrode material.In addition, the present invention passes through the secondary introducing carbon source of substep ball-milling method during the preparation process, it is at low cost, controllability is strong, substep process of thermal treatment ensure that the good crystallinity of material and uniformity, further improve the performance of material, with good economic efficiency and application prospect.
Description
Technical field
The present invention relates to sodium-ion battery positive material technical fields, and in particular to it is compound that a kind of molybdenum ytterbium is co-doped with silicic acid ferrisodium
Electrode material and its preparation method and application.
Background technique
With the increasingly increased fossil energy consumption of the mankind, the environmental problems such as haze, greenhouse effects are got worse.Each national capital
Will the economic model based on fossil fuel to based on new energy based on economic model transformation, Renewable Energy Development and clear
The clean energy is a great strategic task of China's economy and society development.The high speed development of society is to high security, low cost
The demand of energy storage technology is extremely urgent.Currently, lithium ion battery be study most commonly used energy-storage battery using being also, but by
Limited in the reserves of lithium metal, price rises year by year, and the demand of extensive energy storage technology, so that the research of sodium-ion battery
Gradually attract concern.
From cost, energy consumption, resource angularly for, sodium-ion battery is competing with very big market in terms of scale energy storage
Strive advantage.Since the radius ratio lithium ion of sodium ion is big, current research key is that exploitation can stablize quick deintercalation sodium ion
Electrode material.
In many sodium-ion battery positive materials, silicate is because having outstanding chemical stability, and silicon resource is abundant
With advantages of environment protection by favor, but the synthesis of silicic acid ferrisodium is more difficult, and there are still certain limitations for synthesis mode.
Shouding Li et al. people's first passage solid phase method and sol-gal process have synthesized Na2FeSiO4Material, as sodium
When ion battery positive electrode, in 10mA g-1Under current density, 20 weeks capacity of circulation are positively retained at 106mAh g-1(Li S,
Guo J,Ye Z,et al.Zero-strain Na2FeSiO4as novel cathode material for sodium-ion
batteries.ACS applied materials&interfaces,2016,8(27):17233-17238)。Wenhao
Guan et al. has then synthesized Na by sol-gal process2FeSiO4/ C electrode material, material be in three-dimensional cross-linked reticular structure, with
After carbon is compound, the cycle performance of material is obviously improved.In 0.1C (1C=276mA g-1) under current density, 100 circle capacity of circulation
It remains to be maintained at 181mAh g-1, and pure Na2FeSiO4Material then after the circle of circulation 40 capacity attenuation to 100mAh g-1Left and right
(Guan W,Pan B,Zhou P,et al.A high capacity,good safety and low cost Na2FeSiO4-
based cathode for rechargeable sodium-ion battery.ACS applied materials&
interfaces,2017,9(27):22369-22377)。
In addition, CN107492630A discloses a kind of sodium-ion battery flexible electrode material in the application aspect of silicic acid ferrisodium
Material and preparation method thereof and sodium-ion battery, the electrode material include: the carbon nanofiber networks of more carbon nano-fibers composition
Skeleton, and the host material particles being distributed between more carbon nano-fibers, the host material particles can be Na2FeSiO4。
CN108134089A discloses a kind of preparation method of high load amount active material electrode, and this method is in electrode slurry preparation process
Pore creating material is added, the coated equipment blade coating of electrode slurry forms electrode-collector integrated electrode in aluminum foil current collector,
Electrode active material in middle electrode slurry can be ferrosilite sodium.
Although the above method has synthesized silicic acid ferrisodium material, and be applied in electrode material, but silicic acid ferrisodium itself
There are electron conductions it is poor, ion diffusion rates are slow the problems such as, affect it and further apply, it is cyclical stability, forthright again
The chemical properties such as energy still need to be further improved, and synthesis technology is also required to advanced optimize.
Summary of the invention
In order to solve the above technical problems, the present invention provides a kind of molybdenum ytterbiums to be co-doped with silicic acid ferrisodium combination electrode material and its system
Preparation Method and application are modified silicic acid ferrisodium codope and by way of introducing the second phase, effectively improve silicic acid
The chemical property of ferrisodium, has the features such as making it have high conductivity, height ratio capacity, high-rate characteristics and long circulation life
Good application prospect.
In a first aspect, the present invention provides a kind of molybdenum ytterbiums to be co-doped with silicic acid ferrisodium combination electrode material, the combination electrode material
The molecular formula of material is Na2-x-yFeMoxYbySiO4/ C, wherein 0 < x≤0.2,0 < y≤0.2.
The present invention is modified silicic acid ferrisodium using codope and by the way of introducing the second phase.Molybdenum ion and ytterbium ion are total
Material bulk conductivity can be improved with doping, improve its crystal structure, change the flooding mechanism of sodium ion, High valence cation doping can make
Na generate a small amount of vacancy, are conducive to the migration of sodium ion, improve the high rate performance of material；Introducing highly conductive carbon source can be further
Material electronics conductance is improved, while improving material circulation stability.
According to the present invention, the range of x is 0 < x≤0.2 in the molecular formula, for example, can be 0.01,0.01,0.03,
0.05, the specific point value between 0.08,0.1,0.13,0.15,0.18 or 0.2 and above-mentioned numerical value, as space is limited and for letter
Bright consideration, the present invention no longer exclusive list.
According to the present invention, the range of y is 0 < y≤0.2 in the molecular formula, for example, can be 0.01,0.01,0.03,
0.05, the specific point value between 0.08,0.1,0.13,0.15,0.18 or 0.2 and above-mentioned numerical value, as space is limited and for letter
Bright consideration, the present invention no longer exclusive list.
According to the present invention, based on mass percentage, the content of carbon is 1-30% in the combination electrode material, such as can
To be the specific point value between 1%, 5%, 10%, 15%, 20%, 25% or 30% and above-mentioned numerical value, as space is limited and go out
In concise consideration, the present invention no longer exclusive list.
Second aspect, the present invention provides a kind of molybdenum ytterbiums as described in relation to the first aspect to be co-doped with silicic acid ferrisodium combination electrode material
Preparation method, the described method comprises the following steps:
(1) ingredient is carried out in the ratio of each element in molecular formula, sodium source, source of iron, molybdenum source, ytterbium source and silicon source is mixed laggard
Carbon source is added after ball milling for ball milling of row, carries out secondary ball milling, obtains presoma；
(2) presoma that step (1) obtains is heat-treated, obtains the combination electrode material.
According to the present invention, step (1) sodium source is anhydrous sodium acetate, sodium hydroxide, sodium carbonate, sodium oxalate, nitrous acid
Sodium, disodium hydrogen phosphate, sodium bicarbonate, sodium citrate, anhydrous sodium sulfate, odium stearate, enuatrol, sodium tartrate, sodium alginate,
At least one of sodium carboxymethylcellulose, sodium lactate or sodium humate, preferably anhydrous sodium acetate, sodium hydroxide, sodium carbonate,
Or at least one of sodium oxalate, such as can be anhydrous sodium acetate, sodium hydroxide, sodium carbonate, sodium oxalate, sodium nitrite, phosphorus
Sour disodium hydrogen, sodium bicarbonate, sodium citrate, anhydrous sodium sulfate, odium stearate, enuatrol, sodium tartrate, sodium alginate, carboxylic first
Any one in base sodium cellulosate, sodium lactate or sodium humate, typical but non-limiting combination are as follows: anhydrous sodium acetate and hydrogen
Sodium oxide molybdena, sodium carbonate and sodium oxalate, sodium nitrite and disodium hydrogen phosphate, sodium bicarbonate and sodium citrate, anhydrous sodium sulfate and hard
Resin acid sodium, enuatrol and sodium tartrate, sodium alginate and sodium carboxymethylcellulose, sodium lactate and sodium humate etc..
According to the present invention, step (1) source of iron is ferrous oxalate and/or ferrous acetate.
According to the present invention, step (1) molybdenum source is molybdenum dioxide.
According to the present invention, step (1) the ytterbium source is ytterbium oxide.
According to the present invention, step (1) silicon source is silica and/or ethyl orthosilicate.
According to the present invention, step (1) carbon source is glucose, sucrose, fructose, polyethylene glycol, graphene, polyethylene
In alcohol, carbon fiber, soluble starch, coal tar pitch, carbon black, dextrin, coke, cellulose, phenolic resin or carbon nanotube at least
One kind, such as can be glucose, sucrose, fructose, polyethylene glycol, graphene, polyvinyl alcohol, carbon fiber, soluble starch, coal
Any one in pitch, carbon black, dextrin, coke, cellulose, phenolic resin or carbon nanotube, typical but non-limiting group
Be combined into: dextrose and saccharose, fructose and polyethylene glycol, graphene and polyvinyl alcohol, carbon fiber and soluble starch, coal tar pitch and
Carbon black, dextrin and coke, cellulose, phenolic resin and carbon nanotube etc..
Sodium source can be added according to the ratio in molecular formula in step (1) the of the present invention blending process, but in order to
Make up the sodium loss in preparation process, can also excessive addition sodium source, additive amount within 10wt% (relative to sodium source), specifically
Additive amount, which is subject to, synthesizes material requested, as long as reaching the ratio that the sodium content in product meets molecular formula.
According to the present invention, the ball-milling medium that step (1) ball milling and secondary ball milling are added in the process is water, second
At least one of alcohol, ethylene glycol or acetone, such as can be any one in water, ethyl alcohol, ethylene glycol or acetone, it is typical but
Non-limiting combination are as follows: water and ethyl alcohol, ethylene glycol and acetone, water, ethyl alcohol and ethylene glycol etc..
According to the present invention, the mass ratio of abrading-ball and material is (4- during step (1) ball milling and secondary ball milling
20): 1, such as can be specific between 4:1,5:1,8:1,10:1,13:1,15:1,18:1 or 20:1 and above-mentioned numerical value
Point value, as space is limited and for concise consideration, the present invention no longer exclusive list.
According to the present invention, the time of step (1) ball milling be 2-10h, such as can be 2h, 3h, 4h, 5h, 6h,
Specific point value between 7h, 8h, 9h or 10h and above-mentioned numerical value, as space is limited and for concise consideration, the present invention is no longer
Exclusive list.
According to the present invention, the time of step (1) described secondary ball milling is 1-5h, such as can be 1h, 2h, 3h, 4h or 5h,
And the specific point value between above-mentioned numerical value, as space is limited and for concise consideration, the present invention no longer exclusive list.
According to the present invention, step (2) it is described heat treatment carried out under protective atmosphere, the protective atmosphere be nitrogen,
At least one of argon gas or helium.
According to the present invention, the concrete operations of step (2) described heat treatment are as follows: by gained presoma first at 300-500 DEG C
1-10h is kept the temperature, then heats to 500-900 DEG C, keeps the temperature 6-18h.
The mode that above-mentioned substep is heat-treated can make electrode material reaction it is more abundant, have good crystallinity and
Uniformity further improves the chemical property of combination electrode material.
According to the present invention, the temperature being heat-treated for the first time in above-mentioned substep heat treatment process is 300-500 DEG C, such as can be with
It is 300 DEG C, 330 DEG C, 350 DEG C, 380 DEG C, 400 DEG C, 430 DEG C, 450 DEG C, 480 DEG C or 500 DEG C,
And the specific point value between above-mentioned numerical value, as space is limited and for concise consideration, the no longer exhaustive column of the present invention
It lifts.
According to the present invention, the time being heat-treated for the first time in above-mentioned substep heat treatment process is 1-10h, such as be can be
Specific point value between 1h, 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h or 10h and above-mentioned numerical value, as space is limited and for simplicity
The considerations of, the present invention no longer exclusive list.
According to the present invention, the temperature of second heat treatment is 500-900 DEG C in above-mentioned substep heat treatment process, such as can be with
It is 500 DEG C, 550 DEG C, 600 DEG C, 650 DEG C, 700 DEG C, 750 DEG C, 800 DEG C, 850 DEG C or the tool between 900 DEG C and above-mentioned numerical value
Body point value, as space is limited and for concise consideration, the present invention no longer exclusive list.
According to the present invention, the time of second of heat treatment is 6-18h in above-mentioned substep heat treatment process, such as be can be
Specific point value between 6h, 8h, 10h, 12h, 14h, 16h or 18h and above-mentioned numerical value is examined as space is limited and for concise
Consider, the present invention no longer exclusive list.
Molybdenum ytterbium of the present invention is co-doped with the preparation method packet of silicic acid ferrisodium combination electrode material as a preferred technical solution,
Include following steps:
(1) ingredient is carried out in the ratio of each element in molecular formula, sodium source, source of iron, molybdenum source, ytterbium source and silicon source is mixed into postposition
In ball grinder, the mass ratio for controlling abrading-ball and material is (4-20): 1, ball-milling medium is added and carries out a ball milling 2-10h, ball
Carbon source is added after mill, carries out secondary ball milling 1-5h, obtains presoma；
(2) under protective atmosphere, the presoma that step (1) obtains first is kept the temperature into 1-10h at 300-500 DEG C, then
It is warming up to 500-900 DEG C, obtains the combination electrode material after keeping the temperature 6-18h.
The third aspect, the present invention provide the molybdenum ytterbium of one kind as described in relation to the first aspect and are co-doped with silicic acid ferrisodium combination electrode material work
For the application of sodium-ion battery positive material.
Compared with prior art, the present invention at least has the advantages that
(1) present invention is modified silicic acid ferrisodium using molybdenum and ytterbium co-doped, at the same introduce highly conductive carbon source into
Row is compound, and having obtained the molybdenum ytterbium with high conductivity, height ratio capacity, high-rate characteristics and long circulation life, to be co-doped with silicic acid ferrisodium multiple
Composite electrode material.Resulting materials have excellent chemical property, under 1.5-4.0V voltage window, 0.1C current density,
Specific discharge capacity > 188mAh/g, 200 circle capacity retention ratio >=90% of circulation are recycled for the first time.
(2) present invention is during the preparation process by the secondary introducing carbon source of substep ball-milling method, and at low cost, controllability is strong, substep
Process of thermal treatment makes material have good crystallinity and uniformity, further improves the performance of material, the method benefit
In large-scale production, have broad application prospects.
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
The present embodiment provides a kind of molybdenum ytterbiums to be co-doped with silicic acid ferrisodium combination electrode material, the molecular formula of the combination electrode material
For Na1.7FeMo0.2Yb0.1SiO4/ C, is prepared in accordance with the following methods.
(1) anhydrous sodium acetate, ferrous oxalate, molybdenum dioxide, oxidation are weighed according to the molar ratio of each element in molecular formula
Above-mentioned raw materials are mixed and are placed in ball grinder by ytterbium and ethyl orthosilicate, and the mass ratio for controlling abrading-ball and material is 10:1, third
Glucose is added after ball milling by ball milling 2h in ketone, carries out secondary ball milling 5h, obtains presoma, and gained presoma is carried out
It is dry；
(2) in a nitrogen atmosphere, the presoma that step (1) obtains first is kept the temperature into 4h at 350 DEG C, then heats to 900
DEG C, the combination electrode material is obtained after keeping the temperature 10h, the mass fraction of carbon is 10% in the combination electrode material.
Electrochemical property test is carried out using the electrode obtained material as sodium-ion battery positive material, pole piece proportion is electrode
Material: acetylene black: PVDF=80:10:10.Using metallic sodium as reference electrode, CR2025 type button cell is prepared.In 1.5-4.0V
Voltage window, under 0.1C current density, recycling specific discharge capacity for the first time is 200mAh/g, 200 circle capacity retention ratios 93% of circulation.
Embodiment 2
The present embodiment provides a kind of molybdenum ytterbiums to be co-doped with silicic acid ferrisodium combination electrode material, the molecular formula of the combination electrode material
For Na1.8FeMo0.1Yb0.1SiO4/ C, is prepared in accordance with the following methods.
(1) sodium hydroxide, ferrous oxalate, molybdenum dioxide, ytterbium oxide are weighed according to the molar ratio of each element in molecular formula
And silica, above-mentioned raw materials are mixed and are placed in ball grinder, the mass ratio for controlling abrading-ball and material is 4:1, in deionization
Sucrose is added after ball milling by ball milling 10h in water, carries out secondary ball milling 1h, obtains presoma, and gained presoma is done
It is dry；
(2) in a nitrogen atmosphere, the presoma that step (1) obtains first is kept the temperature into 2h at 400 DEG C, then heats to 800
DEG C, the combination electrode material is obtained after keeping the temperature 12h, the mass fraction of carbon is 5% in the combination electrode material.
Electrochemical property test is carried out using the electrode obtained material as sodium-ion battery positive material, pole piece proportion is electrode
Material: acetylene black: PVDF=80:10:10.Using metallic sodium as reference electrode, CR2025 type button cell is prepared.In 1.5-4.0V
Voltage window, under 0.1C current density, recycling specific discharge capacity for the first time is 204mAh/g, 200 circle capacity retention ratios 92% of circulation.
Embodiment 3
The present embodiment provides a kind of molybdenum ytterbiums to be co-doped with silicic acid ferrisodium combination electrode material, the molecular formula of the combination electrode material
For Na1.94FeMo0.05Yb0.01SiO4/ C, is prepared in accordance with the following methods.
(1) according to the molar ratio of each element in molecular formula weigh sodium carbonate, ferrous acetate, molybdenum dioxide, ytterbium oxide and
Above-mentioned raw materials are mixed and are placed in ball grinder by ethyl orthosilicate, and the mass ratio for controlling abrading-ball and material is 20:1, in ethanol
Graphene is added after ball milling by ball milling 4h, carries out secondary ball milling 3h, obtains presoma, and gained presoma is dried；
(2) under an argon atmosphere, the presoma that step (1) obtains first is kept the temperature into 8h at 500 DEG C, then heats to 600
DEG C, the combination electrode material is obtained after keeping the temperature 18h, the mass fraction of carbon is 20% in the combination electrode material.
Electrochemical property test is carried out using the electrode obtained material as sodium-ion battery positive material, pole piece proportion is electrode
Material: acetylene black: PVDF=80:10:10.Using metallic sodium as reference electrode, CR2025 type button cell is prepared.In 1.5-4.0V
Voltage window, under 0.1C current density, recycling specific discharge capacity for the first time is 195mAh/g, 200 circle capacity retention ratios 91% of circulation.
Embodiment 4
The present embodiment provides a kind of molybdenum ytterbiums to be co-doped with silicic acid ferrisodium combination electrode material, the molecular formula of the combination electrode material
For Na1.81FeMo0.17Yb0.02SiO4/ C, is prepared in accordance with the following methods.
(1) anhydrous sodium acetate and sodium oxalate, ferrous oxalate, titanium dioxide are weighed according to the molar ratio of each element in molecular formula
Above-mentioned raw materials are mixed and are placed in ball grinder by molybdenum, ytterbium oxide and ethyl orthosilicate, and the mass ratio for controlling abrading-ball and material is
Phenolic resin is added after ball milling by 15:1, the ball milling 7h in ethylene glycol, carries out secondary ball milling 2h, obtains presoma, and by institute
Presoma is obtained to be dried；
(2) in a nitrogen atmosphere, the presoma that step (1) obtains first is kept the temperature into 6h at 450 DEG C, then heats to 700
DEG C, the combination electrode material is obtained after keeping the temperature 12h, the mass fraction of carbon is 30% in the combination electrode material.
Electrochemical property test is carried out using the electrode obtained material as sodium-ion battery positive material, pole piece proportion is electrode
Material: acetylene black: PVDF=80:10:10.Using metallic sodium as reference electrode, CR2025 type button cell is prepared.In 1.5-4.0V
Voltage window, under 0.1C current density, recycling specific discharge capacity for the first time is 189mAh/g, 200 circle capacity retention ratios 94% of circulation.
Embodiment 5
The present embodiment provides a kind of molybdenum ytterbiums to be co-doped with silicic acid ferrisodium combination electrode material, the molecular formula of the combination electrode material
For Na1.79FeMo0.2Yb0.01SiO4/ C, is prepared in accordance with the following methods.
(1) disodium hydrogen phosphate, ferrous oxalate, molybdenum dioxide, oxidation are weighed according to the molar ratio of each element in molecular formula
Above-mentioned raw materials are mixed and are placed in ball grinder by ytterbium and silica, and the mass ratio for controlling abrading-ball and material is 20:1, go from
Carbon nanotube is added after ball milling by ball milling 10h in sub- water, carries out secondary ball milling 4h, obtains presoma, and by gained presoma
It is dried；
(2) under helium atmosphere, the presoma that step (1) obtains first is kept the temperature into 8h at 450 DEG C, then heats to 650
DEG C, the combination electrode material is obtained after keeping the temperature 12h, the mass fraction of carbon is 15% in the combination electrode material.
Electrochemical property test is carried out using the electrode obtained material as sodium-ion battery positive material, pole piece proportion is electrode
Material: acetylene black: PVDF=80:10:10.Using metallic sodium as reference electrode, CR2025 type button cell is prepared.In 1.5-4.0V
Voltage window, under 0.1C current density, recycling specific discharge capacity for the first time is 198mAh/g, 200 circle capacity retention ratios 91% of circulation.
Embodiment 6
The present embodiment provides a kind of molybdenum ytterbiums to be co-doped with silicic acid ferrisodium combination electrode material, the molecular formula of the combination electrode material
For Na1.78FeMo0.02Yb0.2SiO4/ C, is prepared in accordance with the following methods.
(1) anhydrous sodium sulfate, ferrous oxalate and ferrous acetate, dioxy are weighed according to the molar ratio of each element in molecular formula
Change molybdenum, ytterbium oxide and ethyl orthosilicate, above-mentioned raw materials are mixed and are placed in ball grinder, the mass ratio for controlling abrading-ball and material is
Glucose is added after ball milling by 6:1, the ball milling 5h in ethylene glycol, carries out secondary ball milling 1h, obtains presoma, and by gained
Presoma is dried；
(2) in a nitrogen atmosphere, the presoma that step (1) obtains first is kept the temperature into 2h at 400 DEG C, then heats to 680
DEG C, the combination electrode material is obtained after keeping the temperature 14h, the mass fraction of carbon is 8% in the combination electrode material.
Electrochemical property test is carried out using the electrode obtained material as sodium-ion battery positive material, pole piece proportion is electrode
Material: acetylene black: PVDF=80:10:10.Using metallic sodium as reference electrode, CR2025 type button cell is prepared.In 1.5-4.0V
Voltage window, under 0.1C current density, recycling specific discharge capacity for the first time is 201mAh/g, 200 circle capacity retention ratios 90% of circulation.
Comparative example 1
The molecular formula for the combination electrode material that this comparative example provides is Na1.9FeYb0.1SiO4/ C, in addition to step in preparation process
Suddenly (1) according to the molar ratio of each element in molecular formula weigh anhydrous sodium acetate, ferrous oxalate, ytterbium oxide and ethyl orthosilicate into
Outside row ingredient, other steps and condition are identical with embodiment 1.
Electrochemical property test is carried out using the electrode obtained material as sodium-ion battery positive material, pole piece proportion is electrode
Material: acetylene black: PVDF=80:10:10.Using metallic sodium as reference electrode, CR2025 type button cell is prepared.In 1.5-4.0V
Voltage window, under 0.1C current density, recycling specific discharge capacity for the first time is 180mAh/g, 200 circle capacity retention ratios 86% of circulation.
Comparative example 2
The molecular formula for the combination electrode material that this comparative example provides is Na1.8FeMo0.2SiO4/ C, in addition to step in preparation process
Suddenly (1) weighs anhydrous sodium acetate, ferrous oxalate, molybdenum dioxide and ethyl orthosilicate according to the molar ratio of each element in molecular formula
It carries out outside ingredient, other steps and condition are identical with embodiment 1.
Electrochemical property test is carried out using the electrode obtained material as sodium-ion battery positive material, pole piece proportion is electrode
Material: acetylene black: PVDF=80:10:10.Using metallic sodium as reference electrode, CR2025 type button cell is prepared.In 1.5-4.0V
Voltage window, under 0.1C current density, recycling specific discharge capacity for the first time is 181mAh/g, 200 circle capacity retention ratios 84% of circulation.
Comparative example 3
The molecular formula for the electrode material that this comparative example provides is Na1.7FeMo0.2Yb0.1SiO4, in addition to step in preparation process
(1) directly obtained presoma is heat-treated and (carbon source is not added) outside after first time ball milling, other steps and condition and implementation
Example 1 is identical.
Electrochemical property test is carried out using the electrode obtained material as sodium-ion battery positive material, pole piece proportion is electrode
Material: acetylene black: PVDF=80:10:10.Using metallic sodium as reference electrode, CR2025 type button cell is prepared.In 1.5-4.0V
Voltage window, under 0.1C current density, recycling specific discharge capacity for the first time is 186mAh/g, 200 circle capacity retention ratios 65% of circulation.
Comparative example 4
The molecular formula for the electrode material that this comparative example provides is Na2FeSiO4, in preparation process in addition to step (1) according to point
The molar ratio of each element weighs anhydrous sodium acetate in minor, ferrous oxalate and ethyl orthosilicate carry out outside ingredient and first
Directly obtained presoma is heat-treated and (carbon source is not added) outside after secondary ball milling, other steps and condition and embodiment 1 are completely
It is identical.
Electrochemical property test is carried out using the electrode obtained material as sodium-ion battery positive material, pole piece proportion is electrode
Material: acetylene black: PVDF=80:10:10.Using metallic sodium as reference electrode, CR2025 type button cell is prepared.In 1.5-4.0V
Voltage window, under 0.1C current density, recycling specific discharge capacity for the first time is 154mAh/g, 200 circle capacity retention ratios 52% of circulation.
Comparative example 5
The molecular formula for the combination electrode material that this comparative example provides is Na1.55FeMo0.35Yb0.1SiO4/ C, in preparation process
In addition to step (1) weighs anhydrous sodium acetate, ferrous oxalate, molybdenum dioxide, oxidation according to the molar ratio of each element in molecular formula
Ytterbium and ethyl orthosilicate carry out outside ingredient, other steps and condition are identical with embodiment 1.
Electrochemical property test is carried out using the electrode obtained material as sodium-ion battery positive material, pole piece proportion is electrode
Material: acetylene black: PVDF=80:10:10.Using metallic sodium as reference electrode, CR2025 type button cell is prepared.In 1.5-4.0V
Voltage window, under 0.1C current density, recycling specific discharge capacity for the first time is 170mAh/g, 200 circle capacity retention ratios 62% of circulation.
Comparative example 6
The molecular formula for the combination electrode material that this comparative example provides is Na1.5FeMo0.2Yb0.3SiO4/ C is removed in preparation process
Step (1) according to the molar ratio of each element in molecular formula weighs anhydrous sodium acetate, ferrous oxalate, molybdenum dioxide, ytterbium oxide
And ethyl orthosilicate carries out outside ingredient, other steps and condition are identical with embodiment 1.
Electrochemical property test is carried out using the electrode obtained material as sodium-ion battery positive material, pole piece proportion is electrode
Material: acetylene black: PVDF=80:10:10.Using metallic sodium as reference electrode, CR2025 type button cell is prepared.In 1.5-4.0V
Voltage window, under 0.1C current density, recycling specific discharge capacity for the first time is 169mAh/g, 200 circle capacity retention ratios 60% of circulation.
Comparative example 7
The molecular formula for the combination electrode material that this comparative example provides is Na1.7FeSn0.2Yb0.1SiO4/ C is removed in preparation process
Step (1) according to the molar ratio of each element in molecular formula weigh anhydrous sodium acetate, ferrous oxalate, tin oxide, ytterbium oxide and
Ethyl orthosilicate carries out outside ingredient, other steps and condition are identical with embodiment 1.
Electrochemical property test is carried out using the electrode obtained material as sodium-ion battery positive material, pole piece proportion is electrode
Material: acetylene black: PVDF=80:10:10.Using metallic sodium as reference electrode, CR2025 type button cell is prepared.In 1.5-4.0V
Voltage window, under 0.1C current density, recycling specific discharge capacity for the first time is 176mAh/g, 200 circle capacity retention ratios 74% of circulation.
Comparative example 8
The molecular formula for the combination electrode material that this comparative example provides is Na1.7FeMo0.2Ce0.1SiO4/ C is removed in preparation process
Step (1) according to the molar ratio of each element in molecular formula weighs anhydrous sodium acetate, ferrous oxalate, molybdenum dioxide, cerium oxide
And ethyl orthosilicate carries out outside ingredient, other steps and condition are identical with embodiment 1.
Electrochemical property test is carried out using the electrode obtained material as sodium-ion battery positive material, pole piece proportion is electrode
Material: acetylene black: PVDF=80:10:10.Using metallic sodium as reference electrode, CR2025 type button cell is prepared.In 1.5-4.0V
Voltage window, under 0.1C current density, recycling specific discharge capacity for the first time is 175mAh/g, 200 circle capacity retention ratios 71% of circulation.
Comparative example 9
The molecular formula for the combination electrode material that this comparative example provides is Na1.8FeMo0.1Yb0.1SiO4/ C is removed in preparation process
Presoma is directly warming up to outside 800 DEG C of heat preservation 12h in step (2), other steps and condition are identical with embodiment 2.
Electrochemical property test is carried out using the electrode obtained material as sodium-ion battery positive material, pole piece proportion is electrode
Material: acetylene black: PVDF=80:10:10.Using metallic sodium as reference electrode, CR2025 type button cell is prepared.In 1.5-4.0V
Voltage window, under 0.1C current density, recycling specific discharge capacity for the first time is 187mAh/g, 200 circle capacity retention ratios 88% of circulation.
From the foregoing, it will be observed that the combination electrode material prepared in 1-6 of the embodiment of the present invention has excellent chemical property,
1.5-4.0V voltage window under 0.1C current density, recycles specific discharge capacity > 188mAh/g, 200 circle capacity of circulation for the first time
Conservation rate >=90%.By comparative example 1-4 it is found that when undope Mo, Yb and composite carbon when, the capacity for the first time of combination electrode material
It is decreased obviously with cyclical stability.By comparative example 5-6 it is found that when the too high levels of Mo and Yb, electrode material will lead to
Expect the sharply decline of performance.By comparative example 7 and 8 it is found that when replacing Mo using Sn or being doped using Ce replacement Yb, electrode
The performance raising of material is not obvious, and is illustrated that the Mo adulterated and Yb of the invention can generate synergistic effect, is effectively improved ferrosilite
The chemical property of sodium electrode material.By comparative example 9 it is found that when directly prepared by presoma progress primary heating processing
(not step-by-step processing), capacity and cyclical stability are declined slightly for the first time, illustrate that substep process of thermal treatment can be in certain journey
The chemical property of material is improved on degree.
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 molybdenum ytterbium is co-doped with silicic acid ferrisodium combination electrode material, which is characterized in that the molecular formula of the combination electrode material is
Na2-x-yFeMoxYbySiO4/ C, wherein 0 < x≤0.2,0 < y≤0.2.
2. combination electrode material as described in claim 1, which is characterized in that based on mass percentage, the combination electrode
The content of carbon is 1-30% in material.
3. the preparation method that molybdenum ytterbium as claimed in claim 1 or 2 is co-doped with silicic acid ferrisodium combination electrode material, which is characterized in that
It the described method comprises the following steps:
(1) ingredient is carried out in the ratio of each element in molecular formula, carries out one after sodium source, source of iron, molybdenum source, ytterbium source and silicon source are mixed
Carbon source is added after ball milling for secondary ball milling, carries out secondary ball milling, obtains presoma；
(2) presoma that step (1) obtains is heat-treated, obtains the combination electrode material.
4. method as claimed in claim 3, which is characterized in that step (1) sodium source be anhydrous sodium acetate, sodium hydroxide,
Sodium carbonate, sodium oxalate, sodium nitrite, disodium hydrogen phosphate, sodium bicarbonate, sodium citrate, anhydrous sodium sulfate, odium stearate, oleic acid
At least one of sodium, sodium tartrate, sodium alginate, sodium carboxymethylcellulose, sodium lactate or sodium humate, preferably anhydrous second
At least one of sour sodium, sodium hydroxide, sodium carbonate or sodium oxalate；
Preferably, step (1) source of iron is ferrous oxalate and/or ferrous acetate；
Preferably, step (1) molybdenum source is molybdenum dioxide；
Preferably, step (1) the ytterbium source is ytterbium oxide；
Preferably, step (1) silicon source is silica and/or ethyl orthosilicate；
Preferably, step (1) carbon source be glucose, sucrose, fructose, polyethylene glycol, graphene, polyvinyl alcohol, carbon fiber,
At least one of soluble starch, coal tar pitch, carbon black, dextrin, coke, cellulose, phenolic resin or carbon nanotube.
5. such as the described in any item methods of claim 3-4, which is characterized in that step (1) ball milling and secondary ball milling
The ball-milling medium being added in the process is at least one of water, ethyl alcohol, ethylene glycol or acetone；
Preferably, the mass ratio of abrading-ball and material is (4-20) during step (1) ball milling and secondary ball milling: 1.
6. such as the described in any item methods of claim 3-5, which is characterized in that the time of step (1) ball milling is 2-
10h；
Preferably, the time of step (1) described secondary ball milling is 1-5h.
7. such as the described in any item methods of claim 3-6, which is characterized in that step (2) heat treatment is in protective atmosphere
Lower progress, the protective atmosphere are at least one of nitrogen, argon gas or helium.
8. such as the described in any item methods of claim 3-7, which is characterized in that the concrete operations of step (2) described heat treatment are as follows:
Gained presoma is first kept the temperature into 1-10h at 300-500 DEG C, 500-900 DEG C is then heated to, keeps the temperature 6-18h.
9. such as the described in any item methods of claim 3-8, which is characterized in that the described method comprises the following steps:
(1) ingredient is carried out in the ratio of each element in molecular formula, sodium source, source of iron, molybdenum source, ytterbium source and silicon source is mixed and are placed on ball
In grinding jar, the mass ratio for controlling abrading-ball and material is (4-20): 1, ball-milling medium is added and carries out a ball milling 2-10h, ball milling knot
Carbon source is added after beam, carries out secondary ball milling 1-5h, obtains presoma；
(2) under protective atmosphere, the presoma that step (1) obtains first is kept the temperature into 1-10h at 300-500 DEG C, is then heated up
To 500-900 DEG C, the combination electrode material is obtained after keeping the temperature 6-18h.
10. molybdenum ytterbium as claimed in claim 1 or 2 is co-doped with silicic acid ferrisodium combination electrode material as sodium-ion battery positive material
Application.
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Address after: 065001 No. 1 Fenghua Road, Science and Technology Valley, Langfang Development Zone, Langfang City, Hebei Province Applicant after: Langfang green industry technology service center Applicant after: Institute of process engineering of the Chinese Academy of Sciences Address before: 065001 No. 1 Fenghua Road, Science and Technology Valley, Langfang Development Zone, Langfang City, Hebei Province Applicant before: LANGFANG INSTITUTE OF PROCESS ENGINEERING, CAS Applicant before: Institute of process engineering of the Chinese Academy of Sciences |
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| GR01 | Patent grant | ||
| GR01 | Patent grant |