CN109698326A - A kind of organic phosphorization tin/oxidized graphite composite material for sodium-ion battery cathode - Google Patents
A kind of organic phosphorization tin/oxidized graphite composite material for sodium-ion battery cathode Download PDFInfo
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- CN109698326A CN109698326A CN201710990881.XA CN201710990881A CN109698326A CN 109698326 A CN109698326 A CN 109698326A CN 201710990881 A CN201710990881 A CN 201710990881A CN 109698326 A CN109698326 A CN 109698326A
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- H—ELECTRICITY
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- 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
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
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- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
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- H—ELECTRICITY
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
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- H—ELECTRICITY
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Abstract
The present invention relates to a kind of organic phosphorization tin/oxidized graphite composite materials for sodium-ion battery cathode.The present invention realizes the preparation of material with better simply technique.The beneficial effects of the present invention are: the present invention is using GO material as presoma, with SnCl2·2H2O reaction, forms SnO2@GO composite material.Again using triethylamine as the initiator of polymerization reaction, make hexachlorocyclotriph,sphazene (HCCP), 4,4- dihydroxydiphenylsulisomer that polymerization reaction occur, then PZS is made to coat SnO2@GO realizes carbon coating and phosphatization.Compared with the preparation method of other anode material of lithium-ion batteries, preparation method of the invention is simple and easy to do, better simply to realize the compound of conductive carbon material and Sn-O-P@GN.Sodium-ion battery specific capacity prepared by the present invention is higher, and cyclical stability and high rate performance are excellent.
Description
Technical field
The present invention relates to sodium-ion battery preparation technical fields, and in particular to a kind of anode material of lithium-ion battery and its
Preparation method.
Background technique
With the progress of science and technology and the development of society, it is most important that energy and environmental problem has become the world today
One of project.Fossil fuel is still the current energy most commonly used in the world, however the reserves of fossil energy are limited, the mankind
Increasing demand and the exploitation that restraining is not added, inevitably result in the exhaustion of fossil energy.Therefore, find it is new can be again
The raw energy and scale energy storage are extremely urgent.In many energy storage fields, electrochemical energy storage is that one kind is simply efficiently stored up
It can mode.Wherein, lithium ion battery is the electrochemical power source being widely used at present, but with the industries such as number, traffic to lithium from
Sub- battery relies on aggravation, and limited lithium resource will face shortage problem.Room temperature sodium-ion battery is due to abundant raw material, distribution
Extensively, cheap, the extensive research interest of people is caused, its research and development can be mitigated to a certain extent because of lithium
The battery that shortage of resources causes develops limitation problem.
Anode material of lithium-ion battery mainly includes hard carbon, alloy and ti-based compound at present.Hard carbon is most widely used
A kind of anode material of lithium-ion battery, but since sodium ion radius is larger, in the embedding/de- more difficult of graphite layers, and for the first time
Irreversible SEI passivation layer is easily formed when charge and discharge, first all coulombic efficiencies is caused to reduce, this is to restrict such carbon material to apply
Principal element.There are serious volume expansions during sodium ion intercalation/deintercalation for metal simple-substance or alloy, cause capacity fast
Speed decaying, electrode stability reduce.Titanium-based oxide is by embedded category reaction mechanism as anode material of lithium-ion battery
Carry out storage sodium, however, due in itself crystal structure storage site it is limited, cause this kind of material storage sodium capacity generally lower.
SnO2It is a kind of sodium ion electrode material, but since the volume expansion in its charge and discharge process is larger, leads to material
Crushing, high rate performance and cyclical stability are poor.
Summary of the invention
Aiming at the problems existing in the prior art, the purpose of the present invention is to provide a kind of anode material of lithium-ion batteries
And preparation method thereof, this method is simple and easy, and the anode material of lithium-ion battery specific capacity of preparation is larger, has and preferably follows
Ring stability.
In order to achieve the above object, the present invention is achieved by the following scheme.
(1) a kind of anode material of lithium-ion battery, which is characterized in that including following raw material components: graphene oxide
(GO), hexachlorocyclotriph,sphazene (HCCP), 4,4- dihydroxydiphenylsulisomer, stannous chloride, concentrated hydrochloric acid, triethylamine and solvent.
Preferably, the solvent is methanol, water and ethylene glycol.
Preferably, in the raw material components, the volume ratio of ethylene glycol and water is 8:2.
(2) a kind of preparation method of anode material of lithium-ion battery, which comprises the following steps:
Step 1: 200mg GO being dissolved in the in the mixed solvent of ethylene glycol and water, is mixed, is stirred evenly, mixed
Solution A.
Step 2:1.25g SnCl2·2H2O is dissolved in the in the mixed solvent of the ethylene glycol containing concentrated hydrochloric acid and water to get mixed
Close solution B.
Step 3: solution B being added in solution A, is stirred 40 minutes.Autoclave is put into baking oven, is centrifuged, uses deionization
Then water washing is lyophilized, obtain SnO2@GO。
Step 4:0.15g SnO2@GO is dissolved in 40ml methanol, and ultrasonic 30min obtains solution C.
Step 5:300mgHCCP and 400mg 4,4- dihydroxydiphenylsulisomer are dissolved in 10ml methanol respectively, are added to molten
In liquid C, 5min is stirred, adds triethylamine, stirring is for 24 hours.Reaction time, then, gray precipitate was centrifuged, and washed 3 with methanol
Secondary, vacuum drying obtains PZS@SnO2@GO。
Step 6: by PZS@SnO2@GO calcining, obtains C@Sn-O-P@GN.
Preferably, the volume ratio of the ethylene glycol and water is 8:2 in step 1.
Preferably, the volume ratio of the ethylene glycol and water is 8:2 in step 2；The amount containing concentrated hydrochloric acid is
0.5ml。
Preferably, the temperature of the baking oven is 140 DEG C in step 3, the time of the hydro-thermal is 5h or more.
Preferably, the mode that solution is added is to be added dropwise in step 5；It is described be added triethylamine amount be
1.5ml；The whipping temp is 35 DEG C.
Preferably, during the calcining: the temperature of calcining is 800 DEG C in step 6, the time of the calcining
For 2h, the calcining protective atmosphere is argon gas.Heating rate and rate of temperature fall are 2 DEG C/min in calcining.
Anode material of lithium-ion battery electrochemical property test according to claim 3, it is characterised in that: cathode
Pole piece uses negative electrode active material, and Super P and PVDF (being dissolved in NMP) are uniformly mixed into slurry according to the mass ratio of 80:10:10
It is coated on copper foil after material.100 DEG C in vacuum drying oven, after 12h drying, electrode slice is cut into the disk that diameter is 12mm,
Pole piece load capacity is 1.1-1.5mg/cm2, half-cell, which is tested, to be both less than using CR2032 type button cell in water and partial pressure of oxygen
It is assembled in the glove box of 0.1ppm.Half-cell uses sodium as to electrode, and glass fibre is diaphragm, NaClO4It is dissolved in
Volume ratio is the EC:DEC of 1:1, is used as electrolyte in the solution of 5%FEC.
Compared with prior art, the invention has the benefit that
The present invention is coated SnCl using GO material as presoma2·2H2O forms SnO2@GO.It is polymerization with ethylenediamine
The initiator of reaction makes hexachlorocyclotriph,sphazene (HCCP), 4,4- dihydroxydiphenylsulisomer that polymerization reaction occur, then coat PZS
SnO2@GO realizes carbon coating and phosphatization.Compared with the preparation method of other anode material of lithium-ion batteries, preparation of the invention
Method is simple, better simply to realize the compound of conductive carbon material and Sn-O-P@GN.Preparation method preparation of the invention
Sodium-ion battery specific capacity it is higher, cyclical stability and high rate performance are excellent.
A kind of anode material of lithium-ion battery electrochemical property test, which is characterized in that the sodium-ion battery is by right
It is required that the described in any item carbon-coated phosphorus doping composite materials of 1-3 assemble.
Detailed description of the invention
The present invention has following attached drawing:
Fig. 1 is C@Sn-O-P@GN synthetic schemes；
Fig. 2 is C@Sn-O-P@GN；Sn-O-P glass@GN；PZS@GN；C@Sn-O-P glass；The XRD diagram of C@Sn@GN
Spectrum；
Fig. 3 is the Raman map of C@Sn-O-P@GN；
Fig. 4 is C@Sn@GN and SnO2The hot weight curve of@GN
Fig. 5 is C@Sn-O-P glass@GN scanning electron microscope and transmissioning electric mirror test figure
Fig. 6 is electrochemical property test figure
Specific embodiment
Below in conjunction with attached drawing, invention is further described in detail.
Embodiment 1
200mg GO is dissolved in the in the mixed solvent of ethylene glycol Yu water (volume ratio 8:2), ultrasonic 30min, stirring is
It is even, obtain mixed solution A.Then claim 1.25g SnCl2·2H2O is dissolved in the ethyl alcohol containing 0.5ml concentrated hydrochloric acid (> 5M) and water (body
Product than 8:2) in the mixed solvent to get mixed solution B.Solution B is added in solution A, is stirred 40 minutes.It is put into autoclave
And be transferred into baking oven, 140 DEG C, 5h is then centrifuged for, and is washed with deionized, and is then lyophilized, and SnO is obtained2@GO.It weighs
0.15g SnO2@GO is dissolved in 40ml methanol, and ultrasonic 30min obtains solution C.Weigh 300mgHCCP and 400mg 4,4- dihydroxy
Diphenyl sulphone (DPS) is dissolved in 10ml methanol respectively, is added dropwise in solution C, stirs 5min, adds 1.5ml triethylamine, and 35 DEG C
Stirring is for 24 hours.Reaction time, then, gray precipitate was centrifuged, and was washed 3 times with methanol, and 30 DEG C of vacuum drying 12h or more obtain PZS@
SnO2@GO.By PZS@SnO2800 DEG C of calcining 2h (protecting under argon atmospher) of@GO, obtain C@Sn-O-P@GN.
It is analyzed and characterized
Analysis uses Holland X ' Pert PRO MPD type X-ray diffractometer (XRD, CuK α, λ=0.15406nm) with characterization
Structure, material phase analysis are carried out to sample, surveyed in air atmosphere using German 409 PC Luxx thermogravimetric analyzer (TGA) of STA
The carbon content of test agent.By with Japanese Hitachi S-4800 type scanning electron microscope (SEM) and JEM-2100UHR type
The pattern and structure of transmission electron microscope (TEM) observation sample.Contained element passes through Thermo Scientific in sample
ESCALab250Xi multifunctional light electronics energy disperse spectroscopy (XPS, AlK α) analysis.Using JobinYvon HR800 Raman spectrometer
(Raman) it analyzes and researches to the surface of graphene and composite material in composite material.
As a result it and analyzes:
It is analyzed and characterized
Analysis uses Holland X ' Pert PRO MPD type X-ray diffractometer (XRD, CuK α, λ=0.15406nm) with characterization
Structure, material phase analysis are carried out to sample, surveyed in air atmosphere using German 409 PC Luxx thermogravimetric analyzer (TGA) of STA
The carbon content of test agent.By with Japanese Hitachi S-4800 type scanning electron microscope (SEM) and JEM-2100UHR type
The pattern and structure of transmission electron microscope (TEM) observation sample.Contained element passes through Thermo Scientific in sample
ESCALab250Xi multifunctional light electronics energy disperse spectroscopy (XPS, AlK α) analysis.Using JobinYvon HR800 Raman spectrometer
(Raman) it analyzes and researches to the surface of graphene and composite material in composite material.
As a result it and analyzes:
Fig. 1 elaborates the synthetic schemes of C@Sn-O-P@Graphene material.Firstly, graphite oxidation is obtained graphite oxide
Alkene, then by SnCl2·2H2O is dissolved in the in the mixed solvent of the ethylene glycol containing concentrated hydrochloric acid Yu water (volume ratio 8:2), and oxidation stone
Black alkene mixing, obtains SnO2@GO.HCCP and 4,4- dihydroxydiphenylsulisomer polymerize under the action of triethylamine, and product is added to
It is dissolved in the SnO of methanol2In@GO, PZS@SnO is obtained2@GO obtains C@Sn-O-P@GN through high-temperature calcination.
In order to determine the crystal structure of Sn, we have carried out XRD analysis to product.Fig. 2 be C@Sn-O-P glass@GN,
The XRD spectrum of Sn-O-P glass@GN, PZS@GN, C@Sn-O-P glass and C@Sn@GN.What is synthesized in Fig. 2 is several organic
Phosphatization tinbase carbon material (C Sn-O-P glass GN, Sn-O-P glass GN, C Sn-O-P glass) belongs to amorphous
Glass structure, is not detected apparent lattice structure, and graphene-supported SnO2It grinds and calcines with 4,4- dihydroxydiphenylsulisomer
Product afterwards can be identical with simple substance Sn, this is because graphitic carbon can SnO when temperature is higher than 700 DEG C2It is mono- to be reduced to Sn
Matter.PZS@GN corresponds respectively to (002) and (100) crystal face of graphite in 25.5 ° and 43 ° of two characteristic diffraction peaks.25.5°
The peak at place is more sharp, illustrates that the reducing degree of graphene is higher.
In order to study the degree of graphitization after organic phosphoric acid tinbase carbon material high-temperature calcination, we draw material
The test of graceful spectrum, test results are shown in figure 3.As shown in figure 3, two apparent peaks are respectively in 1343cm-1(D band) and
1585cm-1The ratio of (G band) G band and I band is 0.957, shows that sample reduction degree is higher, shows higher disordering structure,
There is good electric conductivity simultaneously.
In order to probe into the content of metallic tin in organic phosphoric acid tinbase carbon material, we have carried out thermogravimetric curve point to material
It analyses, the content of tin is 58% in C@Sn-O-P glass@GN as shown in Figure 4.
In order to study the microstructure and pattern of composite material, material has been carried out scanning electron microscope and transmission electron microscope by us
It tests (shown in Fig. 5).Fig. 5 (a), 5 (b) be C@Sn-O-P glass@GN scanning electron microscope (SEM) photograph, as can be seen from the figure C@Sn-
O-P glass@GN is made of the porous curling carbon material of gauffer, and any sijna rice corpuscles is can't see on surface.Fig. 5 (c), 5 (d)
It is its transmission electron microscope picture.The nanoparticle of about 10nm or so is shown in figure, but since amorphous structure is presented in material,
Its crystal crack cannot be measured, this is consistent with XRD.This explanation is passed through in the presence of phosphorus and oxygen containing carbon-based material
After high-temperature calcination, coordination occurs for tin and phosphorus, oxygen, generates Sn-O-P glass state material.
C@Sn-O-P glass@GN, PZS@GN, GN, C@Sn-O-P glass and Sn@GN are coated on copper foil simultaneously respectively
It is assembled into button cell in glove box, carries out the test performance measurement of material electrochemical performance.Fig. 5 (a) is C@Sn-O-P
The cyclic voltammetry curve figure of glass@GN, as shown, the reduction peak at 1.93V corresponds to SEI film in circulation for the first time
It being formed, is disappeared in subsequent cyclic process, the peak at 1.55V, 1.20V, 1.91V is attributed to the sodium of P, and 0.367V,
Peak at 0.01V is the alloying reaction of Sn and Na.Oxidation peak at 0.1V and 0.6V is the de- alloying reaction due to Sn.
Oxidation peak at 1.59V, 1.68V, 2.18V is attributed to the gradually removing sodium of P.The repetition of second circle and third circle curve is higher,
Illustrating the electrochemical reaction relatively has very high invertibity.Fig. 5 (b) is the constant current charge-discharge curve of C@Sn-O-P glass@GN,
Electric discharge specific volume is 873.9mAh g for the first time-1, charging specific volume is 366.2mAh g-1, coulombic efficiency 42%, this is attributed to SEI
The formation and high carbon content of film.Fig. 5 (c) is C@Sn-O-P glass@GN, Sn-O-P glass@GN, PZS@GN, GN, C@
Sn-O-P glass is in 100mA g-1Lower 100 circulations, C@Sn-O-P glass@GN specific volume after 100 circulations are
364.2mAh g-1, capacity reserved is 99.3%.Sn@GN and Sn-O-P glass@GN by 100 times circulation after specific volume be
151mAh g-1With 277.4 mAh g-1, capacity reserved is respectively 16.6% and 66.9%, this is because Sn is in charge and discharge
Volume expansion is larger in journey, and carbon coating layer is relatively thin, after repeatedly recycling, caused by Sn is crushed.And PZS@GN and GN
Good cyclical stability is shown, first discharge specific capacity is respectively 484.2mAh g-1With 884.5mAh g-1, fill for the first time
Electric specific capacity is respectively 177.2 mAh g-1With 165.4mAh g-1, coulombic efficiency is respectively 36.6% and 18.9%, shows phosphorus
Doping can expand the interlamellar spacing of graphene, improve electric conductivity, so that sodium ion is quickly inserted into/is inserted and graphene layer,
And then improve the storage amount of receiving and for the first time coulombic efficiency.Fig. 5 (d) C@Sn-O-P glass@GN, Sn@GN, PZS@GN, GN, C@Sn-O-P
Glass is in different current densities (from 100mA g-1To 300mA g-1) under specific capacity, C@Sn-O-P glass@GN electrode exists
100mA g-1、200mA g-1、500mA g-1、1000mA g-1、2000mA g-1、3000mA g-1Under specific discharge capacity difference
For 400mAh g-1、332mAh g-1、288.6mAh g-1、284.6mAh g-1、204.2mAh g-1, when current density is restored to
100mA g-1It and is still 366.8mAh g using 30 circulation specific volumes-1.When current density is restored to 100mA g-1And
It is still 366.8mAh g using 30 circulation specific volumes-1.The high rate performance and C@Sn-O-P glass@of C@Sn-O-P glass
GN's is suitable, but when electric current is restored to 100mA g-1It is recycled using 30 times, specific volume is reduced to 271.7mAh g-1Simultaneously PZS@
GN and GN also has good high rate performance, and especially PZS@GN is in 100mA g-1、200mA g-1、500mA g-1、1000mA
g-1、2000mA g-1、 3000mA g-1Under specific discharge capacity be respectively 182.8mAh g-1、160.2mAh g-1、
134.7mAh g-1、115.8mAh g-1、97mAh g-1, when electric current is restored to 100mA g-1It is recycled using 30 times, specific volume is steady
It is scheduled on 180mAh g-1.And Sn@GN shows very poor multiplying power property, in 100mA g-1、200mA g-1、500mA g-1、
1000mA g-1、2000mA g-1、3000mA g-1Under specific discharge capacity be respectively 373.2mAh g-1、240mAh g-1、
156mAh g-1、110.2mAh g-1、71mAh g-1, when electric current is restored to 100mA g-1It is recycled using 30 times, specific volume is stablized
In 173.7mAh g-1.Fig. 5 (a) is C@Sn-O-P glass@GN in 500mA g-1With 1A g-1Under 1500 long circulatings.For the first time
The specific volume that charges is respectively 306.3m Ah g-1With 289.2Ah g-1, the specific volume after 1500 circulations is respectively 237.1mAh
g-1With 195.2mAh g-1, corresponding capacity reserved is respectively 77.4% and 67.5%.
There is C@Sn-O-P glass@GN good chemical property to be attributed to:
(1) reduced graphene loads Sn particle, and on the one hand electric conductivity that graphene improves composite material is conducive to electronics
Transfer, on the other hand can buffer the volume expansion of Sn；(2) hexa chloro cyclotripolyphosphazene and 4, the polymerization of 4- dihydroxydiphenylsulisomer
Sn particle can be not only coated, carbon-based buffer layer is provided, and phosphorus doping may be implemented, additional specific capacity is provided and is made with Sn
Stablize chemical structure with amorphous Sn-O-P is formed；(3) pass through the association between graphene buffer layers, carbon coating layer and phosphorus doping
Same-action further improves the chemical property of material.
Although the present invention is described in detail with a general description of the specific embodiments in this specification,
But on the basis of the present invention, it can be made some modifications or improvements, such as change the proportion of reactant, change drying temperature, anti-
Between seasonable etc., this will be apparent to those skilled in the art.Therefore, on the basis without departing from spirit of that invention
Upper these modifications or improvements, fall within the scope of the claimed invention.
Claims (3)
1. a kind of organic phosphorization tin/oxidized graphite composite material for sodium-ion battery cathode, it is characterised in that: by 200mg
GO is dissolved in the in the mixed solvent of ethylene glycol Yu water (volume ratio 8:2), and ultrasonic 30min is stirred evenly, and obtains mixed solution A, so
After claim 1.25gSnCl2·2H2O is dissolved in the mixed solvent of the ethylene glycol containing 0.5ml concentrated hydrochloric acid (> 5M) Yu water (volume ratio 8:2)
In to get mixed solution B, solution B is added in solution A, is stirred 40 minutes, is put into autoclave and is transferred into baking oven,
140 DEG C, 5h is then centrifuged for, and is washed with deionized, and is then lyophilized, and obtains SnO2@GO。
2. a kind of organic phosphorization tin/oxidized graphite composite material for sodium-ion battery cathode according to claim 1,
It is characterized by: by 0.15g SnO2@GO is dissolved in 40ml methanol, and ultrasonic 30min obtains solution C, weighs 300mgHCCP and 400mg
4,4- dihydroxydiphenylsulisomers are dissolved in 10ml methanol respectively, are added dropwise in solution C, stir 5min, add 1.5ml tri-
Ethamine causes, and for 24 hours, the reaction time, then, gray precipitate was centrifuged for 35 DEG C of stirrings, is washed 3 times with methanol, 30 DEG C of vacuum drying
12h or more obtains PZS@SnO2@GO, then by PZS@SnO2800 DEG C of calcining 2h (protecting under argon atmospher) of@GO, obtain organic phosphatization
Tin/oxidized graphite composite material C@Sn-O-P@GN.
3. according to a kind of organic phosphorization tin/oxidized graphite composite material for sodium-ion battery cathode as claimed in claim 2,
Be characterized in that: the preparation of the sodium-ion battery cathode is multiple by organic phosphorization tin/graphite oxide claimed in claims 1-2
Condensation material (C@Sn-O-P@GN), acetylene black and Kynoar (PVDF) are weighed according to 8: 1: 1 mass ratio, and three uniformly mixes
Conjunction forms slurry；By slurry even application on copper foil, being put into 100 DEG C of dry 12h in vacuum oven, then by rear electrode slice
Compacting.
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| CN110190270A (en) * | 2019-06-28 | 2019-08-30 | 中国石油大学(华东) | A kind of preparation method and its performance test methods of the titanium composite material for sodium ions to potassium ions battery cathode |
| CN110707308A (en) * | 2019-10-23 | 2020-01-17 | 湖南立方新能源科技有限责任公司 | Negative electrode sodium supplement additive, negative electrode material and sodium ion battery |
| CN110993913A (en) * | 2019-12-06 | 2020-04-10 | 湘潭大学 | Tin phosphide/expanded graphite cathode composite material of sodium ion battery and preparation method thereof |
| CN112928275A (en) * | 2021-01-27 | 2021-06-08 | 鸡西市唯大新材料科技有限公司 | Method for preparing lithium ion carbon negative electrode material by carrying out organic phosphorus modification on carbon black surface |
| CN114420936A (en) * | 2022-03-29 | 2022-04-29 | 太原科技大学 | Nitrogen-doped expanded-layer graphite/tin phosphide multilayer composite material and preparation method thereof |
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| CN114735750A (en) * | 2022-03-24 | 2022-07-12 | 山东能源集团有限公司 | Niobium salt material, preparation method and application thereof |
| CN116130624A (en) * | 2022-12-30 | 2023-05-16 | 浙江维思通新材料有限公司 | Preparation process of composite sodium ion battery anode material |
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