CN106876664A - Anode material for lithium-ion batteries and preparation method thereof and lithium ion battery - Google Patents
Anode material for lithium-ion batteries and preparation method thereof and lithium ion battery Download PDFInfo
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- CN106876664A CN106876664A CN201510909555.2A CN201510909555A CN106876664A CN 106876664 A CN106876664 A CN 106876664A CN 201510909555 A CN201510909555 A CN 201510909555A CN 106876664 A CN106876664 A CN 106876664A
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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
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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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- 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
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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 invention discloses a kind of anode material for lithium-ion batteries and preparation method thereof and lithium ion battery.The method includes：(1) fluorinated phosphate vanadium lithium and pitch are carried out into mechanical fusion, obtains coating；(2) coating is sintered synthesis under inert gas shielding, obtains anode material for lithium-ion batteries.When the anode material for lithium-ion batteries for obtaining is applied to produce the battery core of lithium ion battery, the expansion rate of battery battery core can be effectively reduced, improve the performance of battery.
Description
Technical field
The present invention relates to a kind of anode material for lithium-ion batteries and preparation method thereof and lithium ion battery.
Background technology
At present, the positive electrode based on phosphate radical polyanion has become one of study hotspot, with
The transition metal oxide positive electrode of lithium is compared, and it has preferable security performance, this be primarily due to
Compound based on phosphate radical has structured advantage：It can limit the effusion and burning of oxygen, thus
The security of battery is preferable；Due to the presence of inductive effect, it being capable of producing ratio redox electricity higher
Position；The passage increase of other lithium ion diffusion, it is possible to being well embedded in or removal lithium embedded.This it is main by
In the addition of phosphate anion, oxonium ion is instead of so that the three-dimensional structure of compound changes, make
It has chemical property well and thermodynamic stability and capacity relatively higher.
Wherein LiFePO4 (LiFePO4) is current widely used phosphate cathode material, but its work
Make voltage 3.5V relatively low.Fluorinated phosphate vanadium lithium (LiVPO4F) has discharge voltage higher, can be with
As the lithium ion cell positive phosphate material of more than 4V.
It is few to the research of anode material for lithium-ion batteries LiVPO4F at present.
CN101517790A discloses the novel electrode active material for making active materials for use in secondary electrochemical cells.Wherein
Embodiment 7 specifically discloses preparation LiV (PO4)0.9F1.3Method：In the first step, by metal
The carbothermic reduction reaction of oxide (by taking vanadic anhydride as an example) is made metal phosphate.With mortar and grinding
Rod is pre-mixed the V of 1.82g2O5, 2.64g (NH4)2HPO4With the carbon black of 0.36g, then made
Granulate.Particle is transferred to and is configured with the baking oven of argon gas stream.Heated with 2 DEG C per minute of slow liter of rate
Sample is 700 DEG C until final temperature, and is kept for 16 hours.In the second step, by first step
Obtained vanadium phosphate and other reactant reactions, by the VPO of 1.72g4, 0.0346gLiF and 0.15gNH4F
Premixing, be made it is granular be put into baking oven, be heated to 700 DEG C of final temperature, and be incubated 1 hour.
CN1803593A discloses a kind of preparation of anode material vanadium lithium fluorinated phosphate of lithium ion secondary battery
Method, including：At room temperature, 10% aqueous hydrogen peroxide solution reacts 1- with vanadic anhydride, obtains five
V 2 O colloidal sol, standing forms pentoxide gel；2- adds ammonium dihydrogen phosphate, fluorine in gel
Change lithium and acetylene black well mixed, drying 6h at 100 DEG C obtains precursor in an oven；3- is by precursor
In 25MPa lower sheetings, under inert gas shielding, pre-burning 4h at 300 DEG C, then compressing tablet again,
Under 550 DEG C are protected with argon gas, roasting 1-4h generation LiVPO4F products.The positive electrode that the method is provided
The performance that electrode is obtained can not still meet needs, and when actually carrying out the production of battery battery core, battery core product
Expansion rate it is high, be unsuitable for industrialized production and application.
The anode material for lithium-ion batteries that current prior art is provided is unsuitable for the industrial metaplasia of battery battery core
Produce, it is desirable to provide a kind of anode material for lithium-ion batteries that may be adapted to industrialized production and application.
The content of the invention
Prepared by the anode material for lithium-ion batteries the invention aims to overcome prior art to provide
Battery battery core performance is not enough, and product expansion rate defect high in battery battery core production process, there is provided one
Plant anode material for lithium-ion batteries and preparation method thereof and lithium ion battery.
To achieve these goals, the invention provides a kind of preparation side of anode material for lithium-ion batteries
Method, including：(1) fluorinated phosphate vanadium lithium and pitch are carried out into mechanical fusion, obtains coating；(2) will
The coating is sintered synthesis under inert gas shielding, obtains anode material for lithium-ion batteries.
Present invention also offers one kind as obtained in the method for the present invention lithium ion anode material.
Present invention also offers a kind of lithium ion battery, the lithium ion battery is included by lithium ion of the invention
The battery core that cell positive material is prepared.
The method that the present invention is provided is synthesized using three high temperature sinterings and adds the pitch to carry out mechanical fusion bag
The step of covering, the anode material for lithium-ion batteries for obtaining contains the carbon obtained by pitch sintering, is applied to life
When producing the battery core of lithium ion battery, the expansion rate of battery battery core can be effectively reduced, improve the performance of battery.
Prepare battery half-cell charging capacity can for 168~173mAh/g, discharge capacity can for 139~
144mAh/g, full battery battery core expansion rate can be less than 3%.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Brief description of the drawings
Accompanying drawing is, for providing a further understanding of the present invention, and to constitute the part of specification, with
Following specific embodiment is used to explain the present invention together, but is not construed as limiting the invention.
In accompanying drawing：
Fig. 1 is the preparation method flow chart of anode material for lithium-ion batteries of the invention；
Fig. 2 a are the schematic cross-section of the battery battery core of the production of embodiment 1；
Fig. 2 b are the schematic cross-section of the battery battery core of the production of comparative example 1；
Fig. 3 is the XRD spectra of the anode material for lithium-ion batteries of embodiment 1；
Fig. 4 is the charging and discharging curve of the anode material for lithium-ion batteries of embodiment 1；
Fig. 5 is the SEM image of the anode material for lithium-ion batteries of embodiment 1.
Specific embodiment
Specific embodiment of the invention is described in detail below.It should be appreciated that this place is retouched
The specific embodiment stated is merely to illustrate and explain the present invention, and is not intended to limit the invention.
The present invention provides a kind of preparation method of anode material for lithium-ion batteries, as shown in figure 1, including：
(1) fluorinated phosphate vanadium lithium and pitch are carried out into mechanical fusion, obtains coating；(2) by the cladding
Thing is sintered synthesis under inert gas shielding, obtains anode material for lithium-ion batteries.
, according to the invention it is preferred in the case of, the consumption of the pitch is 0.1 weight of fluorinated phosphate vanadium lithium
%~20 weight %, preferably 1 weight %~12 weight %.
, according to the invention it is preferred in the case of, the softening point of the pitch is more than 200 DEG C；It is preferred that the drip
Green grass or young crops is coal asphalt or petroleum asphalt.It is preferred that the softening point of the pitch is 260~300 DEG C.
In the present invention, machine is carried out after preferably fluorinated phosphate vanadium lithium and pitch being crushed in step (1) again
Tool is merged, the d of fluorinated phosphate vanadium lithium50No more than 30 μm, the d of pitch50No more than 3 μm.
In the present invention, mechanical fusion is carried out in step (1), preferably first by fluorinated phosphate vanadium lithium and drip
Green grass or young crops is pre-mixed under no more than 1000rpm, then fusion cladding is carried out under 2000rpm.
In the present invention, the mechanical fusion is that fluorinated phosphate vanadium lithium is consolidated with pitch under pulverulence
Mix, fluorinated phosphate vanadium lithium can be made to have more preferable mixed effect with pitch, can preferably in step
(2) covered effect of the pitch to fluorinated phosphate vanadium lithium is realized in sintering synthesis, it is final to improve what is prepared
The application effect of anode material for lithium-ion batteries.
, according to the invention it is preferred in the case of, the temperature of the sintering synthesis is 600~900 DEG C, and the time is
2~12h.
A preferred embodiment of the invention prepares fluorinated phosphate vanadium lithium, as shown in figure 1, entering one
Step includes：A () is mixed vanadium source, phosphoric acid root, reducing agent and water to obtain slurry, dry institute
State slurry；B step (a) gained dried object is carried out once sintered synthesis by () under inert gas shielding；
C step (b) the once sintered product of gained is carried out ball milling by () together with lithium fluoride；D () is by step (c)
Gained ball milling product carries out double sintering synthesis under inert gas shielding, obtains fluorinated phosphate vanadium lithium.
, according to the invention it is preferred in the case of, the temperature of the once sintered synthesis and double sintering synthesis is
600~900 DEG C, the time is 2~12h.
, according to the invention it is preferred in the case of, it is 2~8h the times that the ball milling is.
, according to the invention it is preferred in the case of, the vanadium source, phosphoric acid root, between reducing agent and lithium fluoride
Weight ratio be 1：(0.931~1.029)：(0.456~0.504)：(0.228~0.252).
, according to the invention it is preferred in the case of, the vanadium source is ammonium vanadate, vanadium trioxide and five oxidations two
At least one in vanadium, the phosphoric acid root is ammonium dihydrogen phosphate, and the reducing agent is citric acid or sucrose.
Present invention also offers one kind as obtained in the method for the present invention lithium ion anode material.It is wherein main
Material is fluorinated phosphate vanadium lithium, and chemical formula is LiVPO4F, can be determined with XRD method by elder generation and obtained
Spectrogram is obtained, then by spectrogram and document (" Performance Evaluation of Lithium Vanadium
Fluorophosphate in Lithium Metal and Lithium-Ion Cells”,J.Barker,R.k.B.Gover,
P.Burns,et.al.,Journal of the Electrochemical Society,152(9),A1776-A1779,
(2005) XRD spectra of fluorinated phosphate vanadium lithium disclosed in Fig. 1 is contrasted and is determining the lithium ion for obtaining just in)
The main matter of pole material is fluorinated phosphate vanadium lithium.But the lithium ion anode material further comprises and be passed through by pitch
The carbon for providing is sintered, residual carbon is unformed soft carbon after pitch sintering, with good chemical property.Carbon
Content is 0.1 weight %~20 weight % of fluorinated phosphate vanadium lithium, preferably 1 weight %~12 weight %.
Carbon content can be determined by thermogravimetric analysis (TG).
Present invention also offers a kind of lithium ion battery, the lithium ion battery is included by lithium ion of the invention
The battery core that cell positive material is prepared.
, according to the invention it is preferred in the case of, the half-cell charging capacity of the lithium ion battery for 168~
173mAh/g, discharge capacity is 139~144mAh/g, and full battery battery core expansion rate is less than 3%.
Below will the present invention will be described in detail by embodiment.
In following examples and comparative example,
The anode material for lithium-ion batteries of preparation uses SEM methods in the model SU1510 of Tian Mei companies
SEM on obtain the SEM image of the material, with observe preparation lithium ion battery just
The pattern of pole material；
The anode material for lithium-ion batteries of preparation is using XRD method in Japanese Rigaku companies
XRD spectra is determined on D/max-2600/PC, with document (" Performance Evaluation of Lithium
Vanadium Fluorophosphate in Lithium Metal and Lithium-Ion Cells”,J.Barker,
R.k.B.Gover,P.Burns,et.al.,Journal of the Electrochemical Society,152(9),
A1776-A1779, (2005)) in XRD spectra control, it is determined that preparing the chemical constitution of product
It is fluorinated phosphate vanadium lithium；
The half-cell charging capacity of the battery battery core of preparation, discharge capacity parameter are determined by the following method：
Charge-discharge performance test is carried out after the battery battery core of preparation is assembled into 2025 type button cells.Will
Positive electrode, conductive black and binding agent (PVDF) are 90 according to mass ratio:5:5 add N- methyl pyrroles
Anode sizing agent is prepared in pyrrolidone (NMP), the slurry is coated uniformly on positive pole is obtained on aluminium foil
Pole piece.It is cathode pole piece to use metal lithium sheet, and lithium hexafluoro phosphate is electrolyte, and the films of Celgard 2300 are
Barrier film, by anode pole piece, cathode pole piece, lithium hexafluoro phosphate and Celgard in the glove box for be filled with argon gas
2300 films carry out being assembled into 2025 type button cells.
The button cell that will be prepared is in blue electric tester (6 DOF Science and Technology Ltd. of Shenzhen, model
CT2001A 0.1C discharge and recharges are carried out in the voltage range of 3.0V~4.5V on) to measure；
The thickness of battery core after folding core and partial volume during measurement prepares battery battery core, calculates full battery electricity
The expansion rate of core.In battery core thickness after the folded core thickness of measurement and partial volume, three measurement points are set respectively,
With three thickness of measurement point of miking, then average and be listed in Table 1 below, calculated by following formula
To full battery battery core expansion rate：
Full battery battery core expansion rate %=[(the folded core thickness of battery core thickness ﹣ plastic-aluminum film thicknesses ﹣ after partial volume)/
Folded core is thick] × 100%, wherein plastic-aluminum film thickness is 0.3mm；
Illustrated with data in table 1：[(﹣ 7.05 of 7.54 ﹣ 0.3)/7.05] × 100%=2.70%；
[(﹣ 7.07 of 7.58 ﹣ 0.3)/7.07] × 100%=2.97%.
The compound used in following examples and comparative example is by commercially available.
Embodiment 1
This example demonstrates that the preparation method and battery battery core of anode material for lithium-ion batteries of the invention
And battery.
Ammonium dihydrogen phosphate 181.4g, ammonium metavanadate 184.4g, citric acid 90.0g are placed in magnetic agitation,
200ml deionized waters are added, stirring 2h obtains slurry；Slurry is dried at 120 DEG C of temperature, is treated
Sample is crushed after being completely dried, and powder is once burnt at 700 DEG C of sintering temperature under nitrogen protection
Knot 4h；To be cooled down through once sintered powder, add lithium fluoride 44.5g to carry out ball milling, Ball-milling Time is
3h；By ball milling product under nitrogen protection in carrying out double sintering 4h at 700 DEG C of sintering temperature；Will be secondary
Sampling carries out XRD analysis after sintered product cooling, obtains spectrogram as shown in figure 3, compareing determination with document
Consisting of LiVPO4F (fluorinated phosphate vanadium lithium)；It is d to crush50It is 20 μm of powder；
By double sintering product obtained above and pitch carry out mechanical fusion cladding (pitch is coal tar pitch,
Asphalt powder d50It is 1.65 μm, consumption is 1 weight % of double sintering product), coating is obtained, be
Coated double sintering product；The coating is carried out at 750 DEG C of sintering temperature under nitrogen protection
Sintering synthesis 4h, is crushed after product cooling, obtains anode material for lithium-ion batteries.
Obtained anode material for lithium-ion batteries is carried out into electron microscope photographing, as shown in Figure 5, it can be seen that brilliant
Body complete crystallization.
Obtained anode material for lithium-ion batteries is made 5Ah battery battery cores, is obtained as shown in Figure 2 a
Battery battery core expansion be significantly less than in the prior art shown in Fig. 2 b prepare battery battery core.
Table 1 lists the 8 pieces of 5Ah LiVPO4F electricity prepared using above-mentioned anode material for lithium-ion batteries
Pond battery core, carry out folded core thickness (every piece is all 3 average values of measurement result) that thickness measure obtains,
Thickness and the expansion rate being calculated after partial volume.Wherein the average value of expansion rate is 2.70%.
Table 1
| Battery core is numbered | Folded core thickness mm | Battery core thickness mm after partial volume | Expansion rate % |
| 1 | 7.07 | 7.58 | 2.97% |
| 2 | 7.06 | 7.48 | 1.70% |
| 3 | 6.94 | 7.44 | 2.88% |
| 4 | 7.01 | 7.52 | 3.0% |
| 5 | 7.07 | 7.59 | 3.11% |
| 6 | 7.12 | 7.59 | 2.39% |
| 7 | 7.05 | 7.54 | 2.70% |
| 8 | 7.07 | 7.57 | 2.83% |
| Average value | 7.05 | 7.54 | 2.70% |
Charge-discharge performance test is carried out after obtained battery battery core is assembled into 2025 type button cells.
To charging and discharging curve figure as shown in Figure 4, half-cell charging capacity is determined for 168.6mAh/g, electric discharge
Capacity is 140.9mAh/g, and efficiency is 83.6% first.
Embodiment 2
This example demonstrates that the preparation method and battery battery core of anode material for lithium-ion batteries of the invention
And battery.
Ammonium dihydrogen phosphate 217.7g, vanadic anhydride 221.3g, citric acid 108g are placed in magnetic agitation
In, 240ml deionized waters are added, stirring 2h obtains slurry, slurry is dried at 120 DEG C of temperature,
After sample is completely dried crush, powder under nitrogen protection in sintering temperature 600 DEG C once burnt
Knot 12h；To be cooled down through once sintered powder, add lithium fluoride 53.4g to carry out ball milling, Ball-milling Time
It is 8h；By ball milling product under nitrogen protection in carrying out double sintering 2h at 900 DEG C of sintering temperature；By two
Sampling carries out XRD analysis after the cooling of secondary sintered product, determine as described in Example 1 consisting of
LiVPO4F (fluorinated phosphate vanadium lithium), spectrogram is omitted；It is d to crush50=10 μm of powder；
By double sintering product obtained above and pitch carry out mechanical fusion cladding (pitch is coal tar pitch,
Asphalt powder d50Be 3 μm, consumption for double sintering product 4 weight %), obtain coating, be through
The double sintering product of cladding；The coating is burnt at 600 DEG C of sintering temperature under nitrogen protection
12h is combined into, is crushed after product cooling, obtain anode material for lithium-ion batteries.
The anode material for lithium-ion batteries crystal structure obtained according to the method observation in embodiment 1 is intact,
Omit image.
Obtained anode material for lithium-ion batteries is made 5Ah battery battery cores, according to the method for embodiment 1
It is 2.63% to measure full battery battery core expansion rate.Half-cell and full battery testing are carried out, discharge and recharge is omitted bent
Line chart, determines half-cell charging capacity for 172.7mAh/g, and discharge capacity is 143.2mAh/g, first
Efficiency is 83.2%.
Embodiment 3
This example demonstrates that the preparation method of anode material for lithium-ion batteries of the invention.
Ammonium dihydrogen phosphate 272.1g, vanadium trioxide 276.6g, sucrose 135g are placed in magnetic agitation,
300ml deionized waters are added, stirring 2h obtains slurry, slurry is dried at 120 DEG C of temperature, treats
Sample is crushed after being completely dried, and powder is carried out in 900 DEG C of sintering temperature under nitrogen protection once sintered
2h；To be cooled down through once sintered powder, add lithium fluoride 66.8g to carry out ball milling, Ball-milling Time is 2h；
By ball milling product under nitrogen protection in carrying out double sintering 12h at 600 DEG C of sintering temperature；By secondary burning
Sampling carries out XRD analysis after knot product cooling, determines consisting of LiVPO4F as described in Example 1
(fluorinated phosphate vanadium lithium), spectrogram is omitted；It is d to crush50=30 μm of powder；
By double sintering product obtained above and pitch carry out mechanical fusion cladding (pitch is coal tar pitch,
Asphalt powder d50It is 2 μm, consumption is 10 weight % of double sintering synthetic product), coating is obtained,
It is coated double sintering product；The coating is entered at 900 DEG C of sintering temperature under nitrogen protection
Row sintering synthesis 2h, is crushed after product cooling, obtains anode material for lithium-ion batteries.
The anode material for lithium-ion batteries crystal structure obtained according to the method observation in embodiment 1 is intact,
Omit image.
Obtained anode material for lithium-ion batteries is made 5Ah battery battery cores, according to the method for embodiment 1
It is 2.83% to measure full battery battery core expansion rate.Half-cell and full battery testing are carried out, discharge and recharge is omitted bent
Line chart, determines half-cell charging capacity for 168.9mAh/g, and discharge capacity is 139.2mAh/g, first
Efficiency is 82.4%.
Comparative example 1
According to the method for CN1803593A disclosed embodiments 1, LiVPO4F is produced.
Vanadic anhydride 221.3g is taken in beaker, the aqueous hydrogen peroxide solution for Jia 10% thereto
21901ml, after being stirred vigorously, forms the hydrosol；By ammonium dihydrogen phosphate 217.7g, lithium fluoride 53.4g,
And in the above-mentioned hydrosol of surface charcoal 34.06g additions high, after being stirred vigorously 6h, 100 DEG C in an oven
Lower drying 6 hours；Take out, compressing tablet, under argon gas protection, pre-burning 4h at 300 DEG C；Taking-up is pressed again
Piece, 3h is calcined under 550 DEG C, argon gas protection, naturally cools to room temperature, obtains final product LiVPO4F
The LiVPO4F that will be obtained is made 5Ah battery battery cores, and as shown in Figure 2 b, battery battery core is substantially swollen
It is swollen.It is 3.23% that method according to embodiment 1 measures full battery battery core expansion rate.
Obtained battery battery core is carried out into half-cell and full battery testing, charging and discharging curve figure is omitted, it is determined that
Half-cell charging capacity is 139.1mAh/g, and discharge capacity is 130.8mAh/g.
Comparative example 2
Ammonium dihydrogen phosphate 181.4g, ammonium metavanadate 184.4g, citric acid 90.0g are placed in magnetic agitation,
200ml deionized waters are added, stirring 2h obtains slurry, slurry is dried at 120 DEG C of temperature, treats
Sample is crushed after being completely dried, and powder is carried out in 700 DEG C of sintering temperature under nitrogen protection once sintered
Synthesis 4h；To be cooled down through the powder of once sintered synthesis, add lithium fluoride 44.5g to carry out ball milling, ball milling
Time is 3h；By ball milling product under nitrogen protection in carrying out double sintering synthesis at 700 DEG C of sintering temperature
4h；Crushed after product cooling, obtained anode material for lithium-ion batteries.
Obtained anode material for lithium-ion batteries is made 5Ah battery battery cores, half-cell and full battery is carried out
Test, omits charging and discharging curve figure, determines half-cell charging capacity for 153.1mAh/g, and discharge capacity is
125.3mAh/g, first efficiency 81.8%.
The lithium ion cell positive material of present invention offer is provided by above-described embodiment and comparative example result
Using three sintering and cladding synthesis in the preparation process of material, further obtained battery battery core can have more
Good battery performance, illustrates that the method for the present invention can ensure that obtained anode material for lithium-ion batteries has more
Good crystallization, structure is more stable, can preferably play its chemical property.
The process for preparing anode material for lithium-ion batteries from the present invention can further be seen that during this with it is existing
Technology is compared, and fluorinated phosphate vanadium lithium battery aerogenesis is few, and negative reaction is few in illustrating production process, therefore obtains
Full battery battery core expansion rate it is lower, product quality is more preferable.
Claims (10)
1. a kind of preparation method of anode material for lithium-ion batteries, including：
(1) fluorinated phosphate vanadium lithium and pitch are carried out into mechanical fusion, obtains coating；
(2) coating is sintered synthesis under inert gas shielding, obtains lithium ion battery
Positive electrode.
2. method according to claim 1, wherein, the consumption of the pitch is fluorinated phosphate vanadium
0.1 weight %~20 weight % of lithium, preferably 1 weight %~12 weight %.
3. the method according to claim 1 or 3, wherein, the softening point of the pitch is more than 200
℃；It is preferred that the pitch is coal asphalt or petroleum asphalt.
4. method according to claim 1, wherein, the temperature of the sintering synthesis is 600~900
DEG C, the time is 2~12h.
5. the method according to any one in claim 1-4, wherein, further include：
A () is mixed vanadium source, phosphoric acid root, reducing agent and water to obtain slurry, dry described
Slurry；
B step (a) gained dried object is carried out once sintered synthesis by () under inert gas shielding；
C step (b) the once sintered product of gained is carried out ball milling by () together with lithium fluoride；
D step (c) gained ball milling product is carried out double sintering synthesis by () under inert gas shielding,
Obtain fluorinated phosphate vanadium lithium.
6. method according to claim 5, wherein, the once sintered synthesis and double sintering
The temperature of synthesis is 600~900 DEG C, and the time is 2~12h；The time of the ball milling is 2~8h.
7. method according to claim 1, wherein, the vanadium source, phosphoric acid root, reducing agent
Weight ratio and lithium fluoride between is 1：(0.931~1.029)：(0.456~0.504)：(0.228~
0.252)；The vanadium source is at least one in ammonium metavanadate, vanadium trioxide and vanadic anhydride, institute
Phosphoric acid root is stated for ammonium dihydrogen phosphate, the reducing agent is citric acid or sucrose.
8. lithium ion cell positive obtained in a kind of method in 1-7 as claim described in any one
Material.
9. a kind of lithium ion battery, the lithium ion battery is included as the lithium-ion electric described in claim 8
The battery core that pond positive electrode is prepared.
10. lithium ion battery according to claim 9, wherein, half electricity of the lithium ion battery
Pond charging capacity is 168~173mAh/g, and discharge capacity is 139~144mAh/g, and full battery battery core is swollen
Swollen rate is less than 3%.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108134077A (en) * | 2017-12-28 | 2018-06-08 | 清远佳致新材料研究院有限公司 | A kind of anode material for high-voltage lithium ion of nucleocapsid and preparation method thereof |
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| CN108232168A (en) * | 2018-01-19 | 2018-06-29 | 河北力滔电池材料有限公司 | Modified phosphate iron lithium composite material and preparation method |
| CN108232168B (en) * | 2018-01-19 | 2020-06-09 | 河北力滔电池材料有限公司 | Modified lithium iron phosphate composite material and preparation method thereof |
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