CN103985872B - A kind of preparation method and applications of vanadium phosphate sodium lithium anode material - Google Patents
A kind of preparation method and applications of vanadium phosphate sodium lithium anode material Download PDFInfo
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- CN103985872B CN103985872B CN201410257342.1A CN201410257342A CN103985872B CN 103985872 B CN103985872 B CN 103985872B CN 201410257342 A CN201410257342 A CN 201410257342A CN 103985872 B CN103985872 B CN 103985872B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The present invention relates to positive electrode technical field, be specifically related to the preparation method and applications of a kind of vanadium phosphate sodium lithium anode material, it comprises the following steps: A: weighs lithium source, sodium source, vanadium source and phosphate according to mol ratio, weighs citric acid；B: the lithium source weighed, sodium source, vanadium source and phosphate addition deionized water is adjusted to rheology phase, reacts 0.5 2h；C: the citric acid solution of preparation 10% 80%, being added by citric acid solution in the raw material of step B, 60 DEG C 100 DEG C add thermal agitation to solid phase, put in inert atmosphere stove and be warming up to 600 900 DEG C with the speed of 1 10 DEG C/min after drying at 100 DEG C 150 DEG C, constant temperature 6 18 h, after cooling and get final product.The present invention uses a large amount of sodium source to replace lithium source, not only makes the utilization rate of lithium effectively improve, and finally makes material crystalline structure change.The vanadium phosphate sodium lithium anode material good cycling stability that the present invention prepares, high rate performance is excellent.
Description
Technical field
The present invention relates to positive electrode technical field, be specifically related to a kind of vanadium phosphate sodium lithium anode material preparation method and
Its application.
Background technology
The progress in modern epoch, consuming device constantly minimizes, multifunction, and the requirement for battery accordingly also exists
Improve constantly.Lithium ion battery has many advantages: voltage platform is high, and specific capacity is high, has extended cycle life, and self discharge is low, without note
Recall effect etc., electric automobile and energy storage device have huge application prospect.
Stratiform lithium cobaltate cathode material is commonly used commercial Li-ion battery positive electrode.But due to cobalt price
Expensive and poisonous, cyclical stability is poor, can decompose with time overheated overcharging, and may cause battery explosion, exists potential
Safety factor, so always searching for can substitute for the positive electrode of cobalt acid lithium.
In recent years, a kind of new positive electrode-phosphoric acid vanadium lithium, it is continuously available the concern of people.China's vanadium resource and rich
Richness, is vanadium resource reserves big countries, utilizes the vanadium resource of China's abundant, and synthesis of lithium ion battery anode material vanadium lithium phosphate will tool
There are great social effect and economic benefit.
Li3V2 (PO4) 3 crystal has two kinds of space structures, i.e. monoclinic form A-Li3V2 (PO4) 3 and rhombic form B-
Li3V2(PO4)3.Both there is identical cage structure unit V2 (PO4) 3, but metal octahedron VO6 and phosphate anion
The position that the connected mode of tetrahedron PO4 exists with Li is different.Due to existing li-ion systems electrolyte electrochemical window
Limit (≤4.35V) so that the discharge and recharge scope control of phosphoric acid vanadium lithium is at 3.0-4.3V, corresponding to 3 in the middle of Li3V2 (PO4) 3
2 lithium ion deintercalations in individual lithium ion, cause the waste of lithium resource.Research to phosphoric acid vanadium lithium at present is concentrated mainly on list
The phosphoric acid vanadium lithium of biassed fabric, but monocline Li3V2 (PO4) 3 occurs 3 charge and discharge platform in 3.0-4.3V voltage range, no
The most actually used.The Mechanism of electrochemical behaviors of anhydrous of rhombic form Li3V2 (PO4) 3 is fairly simple, shows the typical case two of electrochemical reaction
Phase behavior, 1mol Li3V2 (PO4) 3 can deviate from nearly 2mol Li+, and corresponding voltage platform is 3.76V.But due to orthorhombic
Type phosphoric acid vanadium lithium poor stability, so being difficult to the rhombic form phosphoric acid vanadium lithium being directly synthesized.It addition, phosphoric acid vanadium lithium in prior art
The problems such as the utilization rate of lithium is only 66.7% in preparation process, the waste of the lithium existed.
Summary of the invention
It is an object of the invention to the deficiency overcoming prior art to exist, it is provided that a kind of low cost, the high phosphorus of utilization rate of lithium
Acid vanadium sodium lithium anode material Li2NaV2(PO4)3Preparation method, the circulation of vanadium phosphate sodium lithium anode material that the method is prepared is steady
Qualitative good, high rate performance is excellent.
The purpose of the present invention is achieved through the following technical solutions: the preparation method of a kind of vanadium phosphate sodium lithium anode material, bag
Include following preparation process:
Step A: according to the mol ratio of lithium, sodium, vanadium and phosphate radical in the chemical formula of vanadium phosphate sodium lithium weigh lithium source, sodium source,
Vanadium source and phosphate, weigh citric acid according to the amount accounting for above-mentioned total raw material mass fraction 20%-120%, and the citric acid of the present invention is adopted
With anhydrous citric acid or Citric Acid Mono, mass fraction here refers to anhydrous citric acid；
Step B: the lithium source weighed, sodium source, vanadium source and phosphate addition deionized water is adjusted to rheology phase, reacts 0.5-
2h；
Step C: the citric acid weighed is configured to the citric acid solution that mass concentration is 10%-80%, by citric acid solution
Adding in the reaction raw materials of step B, 60 DEG C-100 DEG C add thermal agitation to solid phase, put into indifferent gas after drying at 100 DEG C-150 DEG C
Atmosphere stove is warming up to 600-900 DEG C with the speed of 1-10 DEG C/min, constant temperature 6-18 h, i.e. obtain vanadium phosphate sodium lithium positive pole material after cooling
Material.
Lithium source in described step A is lithium hydroxide, lithium fluoride, lithium nitrate, lithium carbonate, any one in lithium acetate.
Sodium source in described step A is in sodium nitrate, sodium carbonate, sodium acid carbonate, sodium acetate, sodium oxalate, sodium chloride
Kind.
Vanadium source in described step A is V2O5, VO2, V2O3, NH4VO3In any one.
Phosphate in described step A is ammonium dihydrogen phosphate, diammonium hydrogen phosphate, any one in ammonium phosphate.
Inert gas in described step C is any one in nitrogen and argon gas.
The cooling of described step C is specially and naturally cools to room temperature with stove.
Vanadium phosphate sodium lithium anode material is applied as the positive electrode of lithium ion battery.
The vanadium phosphate sodium lithium of the present invention, its synthesis mechanism is as follows: in material synthesis processes, firstly generates stable orthogonal
(stability sorts vanadium phosphate sodium phase: the orthogonal vanadium phosphate sodium ＞ orthogonal phosphoric acid vanadium lithium of monoclinic lithium vanadium phosphate ＞, so being difficult to the most raw
Produce orthogonal phosphoric acid vanadium lithium), the most orthogonal vanadium phosphate orthogonal phosphoric acid vanadium lithium of sodium inductive formation, then generating orthogonal phosphoric acid vanadium lithium
During, part material reaction generates monoclinic lithium vanadium phosphate.
The present invention compared with prior art, has the advantage that and beneficial effect:
(1) present invention uses rheology phase assisting sol gel method, the most directly prepares based on orthogonal phosphoric acid vanadium lithium
The vanadium phosphate sodium lithium meeting crystalline structure, it has mixing crystalline structure (rhombic form and monoclinic form), consisting of just
Handing over phosphoric acid vanadium lithium, monoclinic lithium vanadium phosphate and orthogonal vanadium phosphate sodium, this material is in charge and discharge process, and orthogonal vanadium phosphate sodium plays surely
Determine the function of material structure；Orthogonal phosphoric acid vanadium lithium, as body of material, undertakes the function of main removal lithium embedded；Monoclinic lithium vanadium phosphate rises
The function terminated to early warning discharge and recharge.Compared to orthogonal phosphoric acid vanadium lithium, its preparation method is simple, compared to monoclinic lithium vanadium phosphate
Three charge and discharge platform, its charge and discharge platform is more beneficial for actual application.
(2) present invention uses a large amount of sodium source to replace lithium source, not only makes the utilization rate of lithium effectively improve, economizes on resources,
Reduce material cost, and be one by the process of quantitative change to qualitative change, finally make material crystalline structure change.
(3) to sum up, the vanadium phosphate sodium lithium anode material good cycling stability that the present invention prepares, high rate performance is excellent.
Accompanying drawing explanation
Fig. 1 is the X-ray diffraction spectrogram of the 1# sample of the embodiment of the present invention 1 preparation.
Fig. 2 is charging and discharging curve and the monocline phosphoric acid of the button half-cell of the 1# sample using the embodiment of the present invention 1 preparation
The charging and discharging curve of the button half-cell of vanadium lithium.
Fig. 3 be the button half-cell of the 1# sample using the embodiment of the present invention 1 preparation cycle performance and discharge and recharge imitate
Rate figure.
Fig. 4 is the X-ray diffraction spectrogram of the 2# sample of the embodiment of the present invention 2 preparation.
Fig. 5 is the charging and discharging curve of the button half-cell of the 2# sample using the embodiment of the present invention 2 preparation.
Fig. 6 be use the embodiment of the present invention 2 preparation 2# sample button half-cell cycle performance.
Fig. 7 is the X-ray diffraction spectrogram of the 3# sample of the embodiment of the present invention 3 preparation.
Fig. 8 is the charging and discharging curve of the button half-cell of the 3# sample using the embodiment of the present invention 3 preparation.
Fig. 9 be use the embodiment of the present invention 3 preparation 3# sample button half-cell cycle performance.
Figure 10 is the X-ray diffraction spectrogram of the 4# sample of the embodiment of the present invention 4 preparation.
Figure 11 is the charging and discharging curve of the button half-cell of the 4# sample using the embodiment of the present invention 4 preparation.
Figure 12 be use the embodiment of the present invention 4 preparation 4# sample button half-cell cycle performance.
Detailed description of the invention:
For the ease of the understanding of those skilled in the art, below in conjunction with embodiment and accompanying drawing, the present invention is made the most in detail
Description, but protection scope of the present invention is not limited to following embodiment.
Embodiment 1.
A kind of preparation method of vanadium phosphate sodium lithium anode material, including following preparation process:
Step A: weigh V according to the ratio of mol ratio 1:1:0.5:32O5, Li2CO3, Na2CO3, NH4H2PO4, according to accounting for
The amount of above-mentioned total raw material mass fraction 29.4% weighs citric acid；
Step B: the V that will weigh2O5, Li2CO3, Na2CO3, NH4H2PO4Add deionized water and be adjusted to rheology phase, reaction
1h；
Step C: the citric acid weighed is configured to the citric acid solution that mass concentration is 35%, adds citric acid solution
In the reaction raw materials of step B, 80 DEG C add thermal agitation to solid phase, put in nitrogen atmosphere stove with 3 DEG C/min's after drying at 120 DEG C
Speed is warming up to 800 DEG C, constant temperature 12h, i.e. obtains vanadium phosphate sodium lithium anode material after naturally cooling to room temperature with stove.
Embodiment 1 obtains vanadium phosphate sodium lithium anode material pulverize and sieve, obtain 1# sample, in FIG, by embodiment 1
The X-ray diffraction spectrogram of the 1# sample of preparation and standard spectrogram carry out contrast and find: 1# sample has mixed phase structure, wherein with just
Friendship phosphoric acid vanadium lithium is main body, hybrid orthogonal vanadium phosphate sodium phase and monoclinic lithium vanadium phosphate phase.
The 1# sample of embodiment 1 gained is made button half-cell as follows.
Concrete, by 1# sample and acetylene black conductor, Kynoar (PVDF) binding agent 85:10:5 in mass ratio
Ratio mixing, be configured to, with 1-METHYLPYRROLIDONE (NMP), slurry that solid content is 46% and be coated in aluminum foil current collector,
Drying, punching, compressing tablet, thus prepare phosphoric acid vanadium lithium electrode.With lithium metal as negative pole, with 1.0mol/L LiPF6(EC:DMC:
EMC=1:1:1 (mol ratio)) it is electrolyte, barrier film is microporous polypropylene membrane, is assembled into button half-cell.
Use the PCBT-138-32D battery controlled testing instrument that Wuhan Lisun Testing Equipment Co., Ltd. produces, button type half
Battery carries out constant current charge-discharge performance test.Charging process is constant-current charge, and restriction voltage is 4.3V (vs. Li/Li+).Electric discharge
Process is constant-current discharge, and blanking voltage is 3.0V (vs. Li/Li+)。
In fig. 2, the charging and discharging curve of button half-cell of 1# sample of embodiment 1 preparation and filling of monoclinic lithium vanadium phosphate
Discharge curve, the charging and discharging curve of button half-cell of the 1# sample of embodiment 1 preparation has 4 charge and discharge platform, wherein with
The platform that at 3.7V, orthogonal phosphoric acid vanadium lithium shows mutually is main body, and this platform capacity accounts for the 93% of total capacity.And it is in 4.15V,
Three platforms of 3.68V and 3.60V are then corresponding to the charge and discharge platform of monoclinic lithium vanadium phosphate, and its total specific capacity accounts for vanadium phosphate sodium lithium
The 7% of specific capacity.Wherein process the charging platform at 4.15V to terminate with early warning charging, be in the discharge platform at 3.6V then
Can indicate that electric discharge terminates.
As seen in Figure 2, the vanadium phosphate sodium lithium that the present invention proposes has with the monoclinic lithium vanadium phosphate being widely studied
Diverse charge and discharge mode (essence is owing to both crystal structures are different).The present invention propose vanadium phosphate sodium lithium have with
3.7V platform is the charge and discharge mode of main body, relative to three more broad charge and discharge platform of monoclinic lithium vanadium phosphate, more has
It is beneficial to reality application.
As seen in Figure 3, under 1C multiplying power (133mA g-1), after vanadium phosphate sodium lithium circulates 100 times, capacity attenuation is the least
(capability retention >=90%), and cyclic process is located all have beyond former circle activation process higher coulombic efficiency (>=
98%).
Embodiment 2.
A kind of preparation method of vanadium phosphate sodium lithium anode material, including following preparation process:
Step A: weigh VO according to the ratio of mol ratio 1:1:0.5:1.52, LiOH, NaNO3, (NH4)2HPO4, according to
The amount accounting for above-mentioned total raw material mass fraction 100% weighs citric acid；
Step B: the VO that will weigh2, LiOH, NaNO3, (NH4)2HPO4Add deionized water and be adjusted to rheology phase, react 2h；
Step C: the citric acid weighed is configured to the citric acid solution that mass concentration is 58%, adds citric acid solution
In the reaction raw materials of step B, 88 DEG C add thermal agitation to solid phase, put in argon gas atmosphere stove with 8 DEG C/min's after drying at 135 DEG C
Speed is warming up to 790 DEG C, constant temperature 16 h, i.e. obtains vanadium phosphate sodium lithium anode material after naturally cooling to room temperature with stove.
Embodiment 2 obtains vanadium phosphate sodium lithium anode material pulverize and sieve, obtains 2# sample, from Fig. 4 it appeared that: 2#
Sample has mixed phase structure, wherein based on orthogonal phosphoric acid vanadium lithium, and hybrid orthogonal vanadium phosphate sodium phase and monoclinic lithium vanadium phosphate phase.
The 2# sample of embodiment 2 gained is made button half-cell as follows.
Concrete, by 2# sample and acetylene black conductor, Kynoar (PVDF) binding agent 85:10:5 in mass ratio
Ratio mixing, be configured to, with 1-METHYLPYRROLIDONE (NMP), slurry that solid content is 46% and be coated in aluminum foil current collector,
Drying, punching, compressing tablet, thus prepare phosphoric acid vanadium lithium electrode.With lithium metal as negative pole, with 1.0mol/L LiPF6(EC:DMC:
EMC=1:1:1 (mol ratio)) it is electrolyte, barrier film is microporous polypropylene membrane, is assembled into button half-cell.
Use the PCBT-138-32D battery controlled testing instrument that Wuhan Lisun Testing Equipment Co., Ltd. produces, button type half
Battery carries out constant current charge-discharge performance test.Charging process is constant-current charge, and restriction voltage is 4.3V (vs. Li/Li+).Electric discharge
Process is constant-current discharge, and blanking voltage is 3.0V (vs. Li/Li+)。
At Fig. 5 it can be seen that the charging and discharging curve of the button half-cell of the 2# sample of embodiment 2 preparation has 4 charge and discharges
Level platform, the platform wherein shown mutually based on orthogonal phosphoric acid vanadium lithium at 3.7V, this platform capacity accounts for total capacity
93%.And be in 4.15V, three platforms of 3.68V and 3.60V then corresponding to the charge and discharge platform of monoclinic lithium vanadium phosphate, its always than
Capacity accounts for the 7% of vanadium phosphate sodium lithium specific capacity.Wherein process the charging platform at 4.15V to terminate with early warning charging, and be in
Discharge platform at 3.6V then can indicate that electric discharge terminates.The vanadium phosphate sodium lithium that the present invention proposes, is more beneficial for actual application.
As seen in Figure 6, under 1C multiplying power (133mA g-1), after vanadium phosphate sodium lithium circulates 100 times, capacity attenuation is the least
(capability retention >=90%), and cyclic process is located all have beyond former circle activation process higher coulombic efficiency (>=
98%).
Embodiment 3.
A kind of preparation method of vanadium phosphate sodium lithium anode material, including following preparation process:
Step A: weigh V according to the ratio of mol ratio 1:2:1:32O3, LiF, CH3COONa, LiH2PO4, on accounting for
The amount stating total raw material mass fraction 90% weighs citric acid；
Step B: the V that will weigh2O3, LiF, CH3COONa, LiH2PO4Add deionized water and be adjusted to rheology phase, reaction
1.5h；
Step C: the citric acid weighed is configured to the citric acid solution that mass concentration is 45%, adds citric acid solution
In the reaction raw materials of step B, 75 DEG C add thermal agitation to solid phase, put in nitrogen atmosphere stove with 5 DEG C/min's after drying at 140 DEG C
Speed is warming up to 790 DEG C, constant temperature 15 h, i.e. obtains vanadium phosphate sodium lithium anode material after naturally cooling to room temperature with stove.
Embodiment 3 obtains vanadium phosphate sodium lithium anode material pulverize and sieve, obtains 3# sample, from Fig. 7 it appeared that: 3# sample
Product have mixed phase structure, wherein based on orthogonal phosphoric acid vanadium lithium, and hybrid orthogonal vanadium phosphate sodium phase and monoclinic lithium vanadium phosphate phase.
The 3# sample of embodiment 3 gained is made button half-cell as follows.
Concrete, by 3# sample and acetylene black conductor, Kynoar (PVDF) binding agent 85:10:5 in mass ratio
Ratio mixing, be configured to, with 1-METHYLPYRROLIDONE (NMP), slurry that solid content is 46% and be coated in aluminum foil current collector,
Drying, punching, compressing tablet, thus prepare phosphoric acid vanadium lithium electrode.With lithium metal as negative pole, with 1.0mol/L LiPF6(EC:DMC:
EMC=1:1:1 (mol ratio)) it is electrolyte, barrier film is microporous polypropylene membrane, is assembled into button half-cell.
Use the PCBT-138-32D battery controlled testing instrument that Wuhan Lisun Testing Equipment Co., Ltd. produces, button type half
Battery carries out constant current charge-discharge performance test.Charging process is constant-current charge, and restriction voltage is 4.3V (vs. Li/Li+).Electric discharge
Process is constant-current discharge, and blanking voltage is 3.0V (vs. Li/Li+)。
In fig. 8, the charging and discharging curve of the button half-cell of the 3# sample of embodiment 3 preparation has 4 charge and discharge platform,
The platform wherein shown mutually based on orthogonal phosphoric acid vanadium lithium at 3.7V, this platform capacity accounts for the 93% of total capacity.And be in
Three platforms of 4.15V, 3.68V and 3.60V are then corresponding to the charge and discharge platform of monoclinic lithium vanadium phosphate, and its total specific capacity accounts for phosphoric acid
The 7% of vanadium sodium lithium specific capacity.Wherein process the charging platform at 4.15V to terminate with early warning charging, and be in the electric discharge at 3.6V
Platform then can indicate that electric discharge terminates.The vanadium phosphate sodium lithium that the present invention proposes, is more beneficial for actual application.
As seen in Figure 9, under 1C multiplying power (133mA g-1), after vanadium phosphate sodium lithium circulates 100 times, capacity attenuation is the least
(capability retention >=90%), and cyclic process is located all have beyond former circle activation process higher coulombic efficiency (>=
98%).
Embodiment 4.
A kind of preparation method of vanadium phosphate sodium lithium anode material, including following preparation process:
Step A: weigh NH according to the ratio of mol ratio 1:1:0.5:1.54VO3, LiNO3, NaCl, (NH4)3PO4, press
Citric acid is weighed according to the amount accounting for above-mentioned total raw material mass fraction 50%；
Step B: the NH that will weigh4VO3, LiNO3, NaCl, (NH4)3PO4Add deionized water and be adjusted to rheology phase, reaction
1h；
Step C: the citric acid weighed is configured to the citric acid solution that mass concentration is 60%, adds citric acid solution
In the reaction raw materials of step B, 70 DEG C add thermal agitation to solid phase, put in argon gas atmosphere stove with 4 DEG C/min's after drying at 130 DEG C
Speed is warming up to 760 DEG C, constant temperature 10h, i.e. obtains vanadium phosphate sodium lithium anode material after naturally cooling to room temperature with stove.
Embodiment 4 obtains vanadium phosphate sodium lithium anode material pulverize and sieve, obtains 4# sample, from Figure 10 it appeared that:
4# sample has mixed phase structure, wherein based on orthogonal phosphoric acid vanadium lithium, and hybrid orthogonal vanadium phosphate sodium phase and monoclinic lithium vanadium phosphate
Phase.
The 4# sample of embodiment 4 gained is made button half-cell as follows.
Concrete, by 4# sample and acetylene black conductor, Kynoar (PVDF) binding agent 85:10:5 in mass ratio
Ratio mixing, be configured to, with 1-METHYLPYRROLIDONE (NMP), slurry that solid content is 46% and be coated in aluminum foil current collector,
Drying, punching, compressing tablet, thus prepare phosphoric acid vanadium lithium electrode.With lithium metal as negative pole, with 1.0mol/L LiPF6(EC:DMC:
EMC=1:1:1 (mol ratio)) it is electrolyte, barrier film is microporous polypropylene membrane, is assembled into button half-cell.
Use the PCBT-138-32D battery controlled testing instrument that Wuhan Lisun Testing Equipment Co., Ltd. produces, button type half
Battery carries out constant current charge-discharge performance test.Charging process is constant-current charge, and restriction voltage is 4.3V (vs. Li/Li+).Electric discharge
Process is constant-current discharge, and blanking voltage is 3.0V (vs. Li/Li+)。
In Fig. 10, the charging and discharging curve of the button half-cell of the 4# sample of embodiment 4 preparation has 4 charge and discharge level
Platform, the platform wherein shown mutually based on orthogonal phosphoric acid vanadium lithium at 3.7V, this platform capacity accounts for the 93% of total capacity.And
Three platforms being in 4.15V, 3.68V and 3.60V then correspond to the charge and discharge platform of monoclinic lithium vanadium phosphate, and its total specific capacity accounts for
The 7% of vanadium phosphate sodium lithium specific capacity.Wherein process the charging platform at 4.15V to terminate with early warning charging, and be at 3.6V
Discharge platform then can indicate that electric discharge terminates.The vanadium phosphate sodium lithium that the present invention proposes, is more beneficial for actual application.
As seen in Figure 11, under 1C multiplying power (133mA g-1), vanadium phosphate sodium lithium circulates after 100 times capacity attenuation very
Little (capability retention >=90%), and cyclic process is located all have beyond former circle activation process higher coulombic efficiency (>=
98%).
Embodiment 5.
A kind of preparation method of vanadium phosphate sodium lithium anode material, including following preparation process:
Step A: weigh V according to the ratio of mol ratio 1:2:0.5:32O5, CH3COOLi, Na2C2O4, (NH4)3PO4, press
Citric acid is weighed according to the amount accounting for above-mentioned total raw material mass fraction 120%；
Step B: the V that will weigh2O5, CH3COOLi, Na2C2O4, (NH4)3PO4Add deionized water and be adjusted to rheology phase, instead
Answer 0.5h；
Step C: the citric acid weighed is configured to the citric acid solution that mass concentration is 10%, adds citric acid solution
In the reaction raw materials of step B, 60 DEG C add thermal agitation to solid phase, put in nitrogen atmosphere stove with 1 DEG C/min's after drying at 100 DEG C
Speed is warming up to 600 DEG C, constant temperature 6h, i.e. obtains vanadium phosphate sodium lithium anode material after naturally cooling to room temperature with stove.
Embodiment 6.
A kind of preparation method of vanadium phosphate sodium lithium anode material, including following preparation process:
Step A: weigh V according to the ratio of mol ratio 1:1:1:32O3, Li2CO3, NaHCO3, (NH4)2HPO4, according to accounting for
The amount of above-mentioned total raw material mass fraction 20% weighs citric acid；
Step B: the V that will weigh2O3, Li2CO3, NaHCO3, (NH4)2HPO4Add deionized water and be adjusted to rheology phase, reaction
2h；
Step C: the citric acid weighed is configured to the citric acid solution that mass concentration is 80%, adds citric acid solution
In the reaction raw materials of step B, 100 DEG C add thermal agitation to solid phase, put in argon gas atmosphere stove with 10 DEG C/min after drying at 150 DEG C
Speed be warming up to 900 DEG C, constant temperature 18 h, i.e. obtain vanadium phosphate sodium lithium anode material after naturally cooling to room temperature with stove.
Above-described embodiment is the present invention preferably embodiment, but embodiments of the present invention are not by above-described embodiment
Limiting, the equivalent variations therefore made according to scope of the present invention patent, within being included in protection scope of the present invention.
Claims (8)
1. the preparation method of a vanadium phosphate sodium lithium anode material, it is characterised in that: include following preparation process:
Step A: weigh lithium source, sodium source, vanadium source according to the mol ratio of lithium, sodium, vanadium and phosphate radical in the chemical formula of vanadium phosphate sodium lithium
And phosphate, weigh citric acid according to the amount accounting for total raw material mass fraction 20%-120%；
Step B: the lithium source weighed, sodium source, vanadium source and phosphate addition deionized water is adjusted to rheology phase, reacts 0.5-2h；
Step C: the citric acid weighed is configured to the citric acid solution that mass concentration is 10%-80%, adds citric acid solution
In the reaction raw materials of step B, 60 DEG C-100 DEG C add thermal agitation to solid phase, put into inert atmosphere stove after drying at 100 DEG C-150 DEG C
In be warming up to 600-900 DEG C with the speed of 1-10 DEG C/min, constant temperature 6-18 h, i.e. obtain vanadium phosphate sodium lithium anode material after cooling.
The preparation method of a kind of vanadium phosphate sodium lithium anode material the most according to claim 1, it is characterised in that: described step
Lithium source in A is lithium hydroxide, lithium fluoride, lithium nitrate, lithium carbonate, any one in lithium acetate.
The preparation method of a kind of vanadium phosphate sodium lithium anode material the most according to claim 1, it is characterised in that: described step
Sodium source in A is the one in sodium nitrate, sodium carbonate, sodium acid carbonate, sodium acetate, sodium oxalate, sodium chloride.
The preparation method of a kind of vanadium phosphate sodium lithium anode material the most according to claim 1, it is characterised in that: described step
Vanadium source in A is V2O5, VO2, V2O3, NH4VO3In any one.
The preparation method of a kind of vanadium phosphate sodium lithium anode material the most according to claim 1, it is characterised in that: described step
Phosphate in A is ammonium dihydrogen phosphate, diammonium hydrogen phosphate, any one in ammonium phosphate.
The preparation method of a kind of vanadium phosphate sodium lithium anode material the most according to claim 1, it is characterised in that: described step
Inert gas in C is any one in nitrogen and argon gas.
The preparation method of a kind of vanadium phosphate sodium lithium anode material the most according to claim 1, it is characterised in that: described step
The cooling of C is specially and naturally cools to room temperature with stove.
8. the positive electrode that prepared by the preparation method of the vanadium phosphate sodium lithium anode material as described in any one of claim 1-7 is made
Positive electrode for lithium ion battery is applied.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410257342.1A CN103985872B (en) | 2014-06-11 | 2014-06-11 | A kind of preparation method and applications of vanadium phosphate sodium lithium anode material |
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