CN108155352A - A kind of anode material for lithium-ion batteries with water resistance and preparation method thereof - Google Patents
A kind of anode material for lithium-ion batteries with water resistance and preparation method thereof Download PDFInfo
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- CN108155352A CN108155352A CN201611111574.1A CN201611111574A CN108155352A CN 108155352 A CN108155352 A CN 108155352A CN 201611111574 A CN201611111574 A CN 201611111574A CN 108155352 A CN108155352 A CN 108155352A
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Abstract
The present invention provides a kind of anode material for lithium-ion batteries with water resistance, the smooth degree on the positive electrode surface and hydrophobic ability significantly increase, chemical property, and especially aerial cyclic curve achieves significant enhancing.The present invention also provides a kind of methods for preparing this anode material for lithium-ion batteries, this method solwution method is in the nickelic tertiary cathode material surface cladding silane coupling agent layer of lithium ion battery, this method processing step is simple and convenient, it is whole easily controllable, and it is environmentally friendly, it is suitble to large-scale industrialized production.
Description
Technical field
The present invention relates to lithium ion battery material technical field, more particularly to a kind of lithium ion battery with water resistance
Positive electrode and preparation method thereof.
Background technology
The theoretical specific capacity of the nickelic tertiary cathode material of lithium ion battery is high, and security performance is high, relative to the electricity of lithium electrode
Gesture is about 4.3V, promises to be the anode material for lithium-ion batteries of a new generation.
However, the nickelic tertiary cathode material of lithium ion battery is since own face pH value is excessively high, in the configuration process of slurry
Middle slurry easy to absorb moisture (absorbing moisture), makes slurry that jelly state be presented, so as to make slurry that can not be coated with, and subsequent pole piece
A large amount of moisture absorptions also result in battery performance and drastically decline, this greatly reduces the industry of the nickelic tertiary cathode material of lithium ion battery
Change degree.
It can be seen that the water resistance of the nickelic tertiary cathode material of lithium ion battery have become this kind of materials industrialization into
One in journey keeps in check greatly.
It would therefore be highly desirable to develop a kind of nickelic tertiary cathode material of lithium ion battery with water resistance and its preparation side
Method.
Invention content
To solve the above-mentioned problems, present inventor has performed sharp study, as a result, it has been found that：With solwution method in lithium ion battery
After nickelic tertiary cathode material surface cladding silane coupling agent layer, the smooth degree and hydrophobic energy on nickelic tertiary cathode material surface
Power significantly increases, chemical property, and especially aerial cyclic curve achieves significant enhancing, so as to complete this
Invention.
The purpose of the present invention is to provide following aspect：
In a first aspect, the present invention provides a kind of anode material for lithium-ion batteries with water resistance, which is characterized in that should
Positive electrode includes nickelic positive electrode ontology and the silane coupling agent layer for being coated on its surface, wherein,
The chemical composition of nickelic positive electrode ontology is LiNixCoyMn1-x-yO2, wherein,
0.5≤x≤0.8,0.1≤y≤0.2,
Silane coupling agent is epoxy group one type of silane coupling agent, selected from Silane coupling agent KH550, silane coupling agent KH560, silicon
It is one or more in alkane coupling agent KH570, silane coupling agent KH580；
Preferably, coating thickness is about 5~30nm.
Second aspect, the present invention also provides a kind of sides for preparing the above-mentioned anode material for lithium-ion batteries with water resistance
Method, which is characterized in that the described method comprises the following steps：
Step 1, silane coupling agent is configured to solution；
Step 2, nickelic positive electrode ontology is added in into silane coupler solution made from step 1, removes solvent；
Step 3, system made from step 2 is heat-treated.
Description of the drawings
Fig. 1 shows that 3K times of SEM figure in the air of sample is made in comparative example 1；
Fig. 2 shows 3K times of SEM figures in the air that sample is made in embodiment 1；
Fig. 3 shows that 8K times of SEM figure in the air of sample is made in comparative example 1；
Fig. 4 shows that 8K times of SEM figure in the air of sample is made in embodiment 1；
Fig. 5 shows the transmission electron microscope picture that embodiment 1 is made under sample 200KV；
Fig. 6 shows the transmission electron microscope picture that embodiment 1 is made under sample 200KV；
Fig. 7 shows that the electronics X ray electronic energy spectrum of sample is made in embodiment 1；
Fig. 8 shows that the granularity graph of sample is made in embodiment 1；
Fig. 9 shows that the granularity graph of sample is made in comparative example 1；
Figure 10 shows that the curve of double curvature of sample is made in embodiment 1 and comparative example 1；
Figure 11 shows that the cyclic curve of sample is made in embodiment 1 and comparative example 1；
Figure 12 shows that the cyclic voltammetry curve of sample is made in embodiment 1 and comparative example 1；
Figure 13 shows that the testing impedance matched curve of sample is made in embodiment 1 and comparative example 1.
Specific embodiment
Below by the present invention is described in detail, the features and advantages of the invention will become more with these explanations
It is clear, clear and definite.
The present invention described below.
According to the first aspect of the invention, a kind of anode material for lithium-ion batteries with water resistance, feature are provided
It is, which includes nickelic positive electrode ontology and the silane coupling agent layer for being coated on its surface, wherein,
The chemical composition of nickelic positive electrode ontology is LiNixCoyMn1-x-yO2, wherein,
0.5≤x≤0.8,0.1≤y≤0.2,
Silane coupling agent is epoxy group one type of silane coupling agent, is preferably selected from Silane coupling agent KH550, silane coupling agent
It is one or more in KH560, silane coupling agent KH570, silane coupling agent KH580.
In the present invention, the nickelic positive electrode ontology is the nickelic ternary of any one lithium ion battery in the prior art
Positive electrode, preferably Li (Ni0.5Co0.2Mn0.3)O2、Li(Ni0.6Co0.2Mn0.2)O2Or Li (Ni0.7Co0.15Mn0.15)O2Deng.
In the present invention, the grain size of the nickelic positive electrode ontology is grain size applicable in the prior art, such as 10~12 μ
M, preferably 10.8~11.8 μm.
In the present invention, the thickness of the silane coupling agent layer be 5~30nm, preferably 10~20nm, most preferably
15nm；.
In the present invention, the anode material for lithium-ion batteries with water resistance, pH are 11~12, preferably
11.5；Specific surface area is 0.4~0.5m2/ g, preferably 0.4348m2/ g, tap density are about 2.4g/cm3, compacted density is
3.4~3.6g/cm3, preferably 3.6g/cm3；
Can be that there are absorption peaks at 101.82eV in combination according to its X ray electron spectrum；
Its first discharge specific capacity discharged under 1C current densities is more than 155mAh/g, is after 100 circle of cycle
More than 138mAh/g, capacity retention ratio are more than 88%.
The chemical property of anode material for lithium-ion batteries is directly related with the water resistance of the material, under normal circumstances,
The water proofing property of anode material for lithium-ion batteries is stronger, and chemical property is more excellent.
According to the second aspect of the invention, it also provides and a kind of prepares the above-mentioned lithium ion cell positive material with water resistance
The method of material, which is characterized in that the described method comprises the following steps：
Step 1, silane coupling agent is configured to solution.
In the present invention, the silane coupling agent is the silane coupling agent described in first aspect present invention.
In the present invention, prepare silane coupler solution used in solvent be Small molecule organic solvents, preferably methanol,
It is one or more in ethyl alcohol, acetone, dichloromethane, chloroform, more preferably methanol and/or ethyl alcohol, most preferably ethyl alcohol.
In the present invention, in silane coupler solution obtained, the volume ratio of silane coupling agent and solvent is 1:(30~
60), preferably 1:(40~55), most preferably 1:50.
It is found in the present invention, when the volume ratio of silane coupling agent and solvent is more than 1:When 30, silane coupler solution is glued
It spends greatly, when carrying out coating modification to nickelic positive electrode ontology using this silane coupling agent, modification lithium-ion electricity obtained
Pond positive electrode surface coating layer it is blocked up in addition reunite it is blocking, hinder movement of the lithium ion between anode or make lithium from
Sub- cell positive material loses powder characteristics, can not in lithium ion battery normal use；When silane coupling agent and the body of solvent
Product is than being less than 1:When 60, the concentration of silane coupler solution is too low, using this silane coupler solution to nickelic positive electrode
When being modified, it is excessively thin or even incomplete to obtain the surface coated silane coupling agent layer of modification lithium-ion battery anode material, leads
Cause modification is insufficient, and water resistance is not strong, and chemical property improves unobvious.
In a kind of preferred embodiment of the present invention, silane coupling agent is promoted in a solvent using the method for manual intervention
Dissolving, it is preferable that using stirring or ultrasonic vibration method, it is further preferable that the method using ultrasonic vibration.
Step 2, nickelic positive electrode ontology is added in into silane coupler solution made from step 1, removes solvent.
In the present invention, the nickelic positive electrode ontology is the nickelic positive electrode sheet described in first aspect present invention
Body.
In the present invention, the envelope-bulk to weight ratio of silane coupler solution and nickelic positive electrode ontology is 50mL:(3~8)
G, preferably 50mL:(4~6) g, most preferably 50mL:5g.
In the present invention, it is molten in removing system after nickelic positive electrode ontology is added in silane coupler solution
Agent makes silane coupling agent equably be coated on nickelic positive electrode body surface,
In a kind of preferred embodiment of the present invention, the method that removes solvent is normal heating method and heating under diminished pressure,
Preferably normal heating method.
The inventors discovered that normal heating method can be such that the solvent in system is evenly removed, and silane coupling agent energy
It is enough to be equably coated on nickelic positive electrode surface, form the anode material for lithium-ion batteries with silane coupling agent layer.
In the present invention, when using the solvent in normal heating method removing system, it is preferable that heating temperature for 50 DEG C~
80 DEG C, preferably 55 DEG C~70 DEG C, more preferably 60 DEG C.
The inventors discovered that when the solvent in the removing system under above-mentioned temperature condition, the evaporation rate of solvent is moderate,
Cladding process is easily controllable, and the clad formed is uniform, stablizes.
In a kind of preferred embodiment of the present invention, constantly system is stirred during solvent is removed.
Step 3, system made from step 2 is heat-treated.
In the present invention, after solvent is removed, trace solvent is inevitably remained in clad, cause clad with
Ontology combines not secured enough, and the thickness of clad is also uneven, and after being heat-treated, in clad micro solvent also by
It eliminates, and coating thickness is more uniformly distributed, clad is combined more close with ontology.
In the present invention, the temperature of heat treatment is 200 DEG C~400 DEG C, preferably 250 DEG C~350 DEG C, more preferably 300
℃。
The inventors discovered that when heat treatment temperature is higher than 400 DEG C, the ratio of modification lithium-ion battery anode material can be caused
Surface area increases, and then it is caused to recycle conservation rate and capacity attenuation, that is, chemical property reduces；And when heat treatment temperature is low
When 200 DEG C, it is impossible to reach the desired effect of heat treatment.
In the present invention, the time of heat treatment is 4~8 hours, preferably 5~7 hours, most preferably 6 hours.
The inventors discovered that when heat treatment time is less than 4 hours, it is impossible to reach the desired effect of heat treatment, work as heat treatment
After time is more than 6 hours, the chemical property of modification lithium-ion battery anode material obtained no longer dramatically increases, and continues to increase
Heat treatment time can reduce production efficiency.
According to anode material for lithium-ion batteries provided by the invention with water resistance and preparation method thereof, have following
Advantageous effect：
(1) positive electrode can effectively reduce the water absorption rate of anode material for lithium-ion batteries；
(2) in addition, surface coated silane coupling agent improves the storge quality of anode material for lithium-ion batteries；
(3) method processing step provided by the invention is simple and convenient, whole easily controllable and environmentally friendly, is suitble to
Large-scale industrialized production.
Embodiment
Embodiment 1
(1) 1mol Li (Ni are weighed0.6Co0.2Mn0.2)O2Presoma and lithium carbonate 0.5mol, they are uniformly mixed, and are mixed
Conjunction mode is mechanical dry mixed, and mixing speed 80rpm stirs 1h, and uniformly mixed mixture is placed into corundum crucible
In be put into Muffle furnace, be passed through 550 DEG C of pre-burning 5h of oxygen, then calcine 20h at 800 DEG C, heating rate is 2 DEG C/min, most
Li (Ni are obtained eventually0.6Co0.2Mn0.2)O2Positive electrode；
(2) it is calculated with silicon covering amount 1000ppm, weighs 0.84g silane coupling agent Kh-560, using absolute ethyl alcohol as molten
Agent, according to volume ratio 50:1 is added dropwise silane coupling agent Kh-560, by solution ultrasonic vibration 2h；
(3) Li (Ni obtained by step 1 are added in the solution after ultrasonic vibration0.6Co0.2Mn0.2)O2Material, in 65 DEG C of oil
Under the conditions of bath, stirring is until evaporation of the solvent is complete；
(4) obtained mixture is heat-treated 6h at 300 DEG C in vacuum drying chamber, it is silane coupled obtains final product
Li (the Ni of agent Kh-560 claddings0.6Co0.2Mn0.2)O2Tertiary cathode material.
In lithium ion anode material obtained with water resistance, the thickness of Kh-560 claddings is 15nm or so, is coated
The median particle diameter D50 of material is 11.38 μm afterwards, and the first discharge specific capacity that sample obtained discharges under 1C current densities is
155.99mAh/g, 100 circle of cycle is later 139.68mAh/g, capacity retention ratio 89.54%.
Embodiment 2
(1) 1mol Li (Ni are weighed0.5Co0.2Mn0.3)O2Presoma and lithium carbonate 0.5mol, they are uniformly mixed, and are mixed
Conjunction mode is mechanical dry mixed, and mixing speed 80rpm stirs 1h, and uniformly mixed mixture is placed into corundum crucible
In be put into Muffle furnace, be passed through 550 DEG C of pre-burning 5h of oxygen, then calcine 20h at 800 DEG C, heating rate is 2 DEG C/min, most
Li (Ni are obtained eventually0.5Co0.2Mn0.3)O2Positive electrode；
(2) it is calculated with silicon covering amount 1000ppm, weighs 0.804g silane coupling agent Kh-570, using absolute ethyl alcohol as molten
Agent, according to volume ratio 50:1 is added dropwise silane coupling agent Kh-570, by solution ultrasonic vibration 2h；
(3) Li (Ni obtained by step 1 are added in the solution after ultrasonic vibration0.5Co0.2Mn0.3)O2Material, in 65 DEG C of oil
Under the conditions of bath, stirring is until evaporation of the solvent is complete；
(4) obtained mixture is heat-treated 6h at 300 DEG C in vacuum drying chamber, it is silane coupled obtains final product
Li (the Ni of agent Kh-570 claddings0.5Co0.2Mn0.3)O2Tertiary cathode material.
In lithium ion anode material obtained with water resistance, the thickness of Kh-570 claddings is 12nm or so, is coated
The median particle diameter D50 of material is that the first discharge specific capacity that sample made from 11.34 μm discharges under 1C current densities is afterwards
157.34mAh/g, 100 circle of cycle is later 138.72mAh/g, capacity retention ratio 88.2%.
Embodiment 3
(1) the commercially available Li (Ni of 1mol are weighed0.5Co0.2Mn0.3)O2With 0.84g silane coupling agent Kh-560, made with absolute ethyl alcohol
For solvent, according to volume ratio 50:1 is added dropwise silane coupling agent Kh-560, by solution ultrasonic vibration 2h；
(2) Li (Ni obtained by step 1 are added in the solution after ultrasonic vibration0.5Co0.2Mn0.3)O2Material, in 65 DEG C of oil
Under the conditions of bath, stirring is until evaporation of the solvent is complete；
(3) obtained mixture is heat-treated 6h at 300 DEG C in vacuum drying chamber, it is silane coupled obtains final product
Li (the Ni of agent Kh-560 claddings0.5Co0.2Mn0.3)O2Tertiary cathode material.
In lithium ion anode material obtained with water resistance, the thickness of Kh-560 claddings is 13nm or so, is coated
The median particle diameter D50 of material is 11.42 μm afterwards, and the first discharge specific capacity that sample obtained discharges under 1C current densities is
155.34mAh/g, 100 circle of cycle is later 140.52mAh/g, capacity retention ratio 90.45%.
Comparative example
Comparative example 1
This comparative example used sample is Li (Ni obtained in 1 step 1 of embodiment0.6Co0.2Mn0.2)O2Positive electrode.
It is 114.81mAh/g that the first discharge specific capacity that sample discharges under 1C current densities, which is made, in comparative example 1, is recycled
100 circle after specific discharge capacity be 101.91mAh/g, capacity retention ratio 88.76%.
Comparative example 2
This comparative example used sample is Li (Ni obtained in 2 step 1 of embodiment0.5Co0.2Mn0.3)O2Positive electrode.
It is 116.57mAh/g that the first discharge specific capacity that sample discharges under 1C current densities, which is made, in comparative example 2, is recycled
100 circle after specific discharge capacity be 99.47mAh/g, capacity retention ratio 85.33%.
Comparative example 3
This comparative example used sample is the commercially available Li (Ni used in embodiment 30.5Co0.2Mn0.3)O2Positive electrode.
It is 116.57mAh/g that the first discharge specific capacity that sample discharges under 1C current densities, which is made, in comparative example 3, is recycled
100 circle after specific discharge capacity be 100.24mAh/g, capacity retention ratio 85.99%.
Experimental example
The scanning electron microscope analysis of 1 sample of experimental example
This experimental example used sample is made for embodiment 1 and comparative example 1.
Above-mentioned sample is placed in air, carries out 3K times of SEM test, as a result as depicted in figs. 1 and 2, wherein,
Fig. 1 shows that 3K times of SEM figure in the air of sample is made in comparative example 1；
Fig. 2 shows 3K times of SEM figures in the air that sample is made in embodiment 1；
Above-mentioned sample is placed in air again, carries out 8K times of SEM test, as a result as shown in Figure 3 and Figure 4, wherein,
Fig. 3 shows that 8K times of SEM figure in the air of sample is made in comparative example 1；
Fig. 4 shows that 8K times of SEM figure in the air of sample is made in embodiment 1；
By Fig. 1~Fig. 4 it is found that the coating thickness on the surface of sample is more uniform, but sample surfaces sponginess is still
There is certain difference, smooth more in surface of sample are made than comparative example 1 for sample made from embodiment 1, not by any theory
Constraint, inventors believe that this moisture that may have been adsorbed with comparative example 1 in air is related.
The transmission electron microscope analysis of 2 sample of experimental example
This experimental example used sample is made for embodiment 1.
Above-mentioned sample is subjected to transmissioning electric mirror test under the conditions of 200KV, as a result as shown in Figure 5 and Figure 6, wherein,
Fig. 5 shows the transmission electron microscope picture that embodiment 1 is made under sample 200KV；
Fig. 6 shows the transmission electron microscope picture that embodiment 1 is made under sample 200KV；
By Fig. 5 and Fig. 6 it is found that in Li (Ni0.6Co0.2Mn0.2)O2It is even that material surface forms one layer of more uniform silane
Join agent Kh-560, wherein, the thickness that Kh-560 layers of clad silane coupling agent is probably in 15nm or so.
The X ray electron spectroscopy analysis of 3 sample of experimental example
This experimental example used sample is made for embodiment 1.
Above-mentioned sample is subjected to X ray electron spectrum test, the results are shown in Figure 7, as shown in Figure 7, can be in combination
There are an absorption peaks at 101.82eV.
With Si in database4+Normal data compare, find its respectively with Si4+2p electronics combination can it is identical, because
This, inventors believe that Li (Ni0.6Co0.2Mn0.2)O2Material surface cladding is Si4+。
The physical and chemical performance analysis of 4 sample of experimental example
This experimental example used sample is made for embodiment 1 and comparative example 1.
The granularmetric analysis result of sample and other physical function parameters are as shown in Table 1 and Table 2.
The granularmetric analysis of 1 sample of table
In table 2, D10 represents D10 grain sizes, and D25 represents D25 grain sizes, and D50 represents D50 grain sizes, and D75 represents D75 grain sizes,
D90 represents D90 grain sizes, and Dmax represents maximum particle diameter.
As shown in Table 1, embodiment 1 is made the grain size of sample and more concentrates, and good particle diameter distribution is more uniformly distributed.
The physical property of 2 sample of table
| Sample | pH | BET(m2/g) | Moisture (ppm) | Tap density (g/cm3) | Compacted density (g/cm3) |
| Embodiment 1 | 11.5 | 0.4348 | 176.9 | 2.4 | 3.6 |
| Embodiment 2 | 11.24 | 0.4671 | 163.4 | 2.4 | 3.5 |
| Embodiment 3 | 11.27 | 0.4531 | 187.7 | 2.4 | 3.4 |
| Comparative example 1 | 11.06 | 0.5365 | 356.7 | 2.1 | 3.2 |
| Comparative example 2 | 11.18 | 0.4952 | 378.3 | 2.2 | 3.2 |
| Comparative example 3 | 11.18 | 0.4952 | 378.3 | 2.2 | 3.2 |
In table 2, pH represents the pH value of sample, and BET shows the specific surface area of sample, and moisture shows moisture in sample.
As shown in Table 2, the tap density of sample is made in embodiment 1, wanting for sample is made in compacted density relative contrast example 1
Height, BET is less than normal, and contained humidity is on the low side.
The PH that sample is made in embodiment 1 is more higher, is 11.5, the general nickelic tertiary cathode material PH of lithium ion battery is less than
11, it is likely that positive electrode is caused to analyse lithium in charge-discharge test, capacity attenuation is then caused and reduces battery performance.
Fig. 8, Fig. 9 are respectively the granularity graph that sample is made in embodiment 1 and comparative example 1.
From Fig. 8 and Fig. 9 it is found that compared with sample is made in comparative example 1, embodiment 1 be made the size dispersity of sample compared with
Good, size distribution is more uniform, and sample is made with the presence of little particle in comparative example 1, causes size distribution uneven.
The curve of double curvature analysis of 5 sample of experimental example
This experimental example used sample is made for embodiment 1 and comparative example 1.
Above-mentioned sample first under the current density of 0.1C is activated, then carries out the test of charge and discharge again, as a result such as
Shown in Figure 10.
As shown in Figure 10, when activating for the first time, the specific discharge capacity outline that sample is made in comparative example 1 is made higher than embodiment 1
Obtain the specific discharge capacity of sample.
In multiplying power test under the current density of 0.5C, 1C, 2C, 3C and 5C, the electric discharge specific volume of sample is made in embodiment 1
Amount is all respectively higher than comparative example 1 and specific discharge capacity of the sample under corresponding current density is made, and difference is increasing.
Without being bound by any theory, inventors believe that, silane coupling agent Kh-560 belongs to silane derivative, itself has
There is hydrophobicity, when silane coupling agent Kh-560 is coated on Li (Ni0.6Co0.2Mn0.2)O2Material surface forms netted clad structure
When, the moisture that can completely cut off in air leads to the drastically decline of material electrochemical performance in the absorption of material surface.
And silane coupling agent Kh-560 cladding tertiary cathode material Li (Ni0.6Co0.2Mn0.2)O2It is formed on its surface
One layer of inertia clad, improves the stability of the structure of material, and inertia clad can inhibit to be electrolysed in charge and discharge process
The HF acid generated in liquid is to anode material for lithium-ion batteries ontology Li (Ni0.6Co0.2Mn0.2)O2It corrodes.
Silane coupling agent Kh-560 clads are also prevented from anode material for lithium-ion batteries ontology Li
(Ni0.6Co0.2Mn0.2)O2It dissolves in the electrolytic solution,
In addition, there are-Si-O-C- keys ,-C-O-C- keys and epoxy bond in silane coupling agent Kh-560, as silane coupling agent Kh-
560 are coated on material surface when forming netted clad structure, and oxygen atom has two pairs of lone pair electrons, may be in Li
(Ni0.6Co0.2Mn0.2)O2Material surface forms a quick electron transfer pathways, increases electron transfer rate, so as to improve
The charge-discharge performance of material.
The cyclic curve analysis of 6 sample of experimental example
This experimental example used sample is made for embodiment 1 and comparative example 1.
The cyclic curve in above-mentioned sample placement air is tested, as a result as shown in figure 11 wherein,
Curve 1 represents that the cyclic curve of sample is made in embodiment 1；
Curve 2 represents that the cyclic curve of sample is made in comparative example 1.
As shown in Figure 11, the first discharge specific capacity that comparative example 1 is made that sample discharges under 1C current densities is
114.81mAh/g, cycle 100 circle after specific discharge capacity be 101.91mAh/g, capacity retention ratio 88.76%；
And it is 155.99mAh/g that the first discharge specific capacity that sample discharges under 1C current densities, which is made, in embodiment 1, cycle
It is 135.03mAh/g, capacity retention ratio 86.88% after 100 circles.
After exposure in air, for two kinds of samples when electrochemistry recycles, cycle conservation rate has been held at one
Relatively smoothly in level, but compared with the specific discharge capacity of sample is made in comparative example 1, embodiment 1 is made sample and is recycling
Specific capacity is higher by 35mAh/g after 200 circles, this shows that the processing of silane coupling agent Kh-560 effectively improves lithium ion battery height
The water absorption issue of nickel tertiary cathode material improves the hydrophobicity of material on the whole.
The cyclic voltammetry curve analysis of 7 sample of experimental example
This experimental example used sample is made for embodiment 1 and comparative example 1.
The cyclic voltammetry curve in above-mentioned sample placement air is tested, sweeps speed as 0.1mV/s, as a result as shown in figure 12,
In,
Curve 1 represents that the cyclic voltammetry curve of sample is made in embodiment 1；
Curve 2 represents that the cyclic voltammetry curve of sample is made in comparative example 1.
As shown in Figure 12, CV curves (cyclic voltammetry curve) shape of both samples is similar, wherein mainly there is three pairs of oxygen
Change reduction peak, oxidation peak is respectively 3.76V, 4.02V and 4.25V or so, these three correspond to lithium ion battery stratiform three respectively
First anode Li (Ni0.6Co0.2Mn0.2)O2Transformation (H1/M) of the material from hexagonal phase to monoclinic phase, the transformation of the opposite hexagonal phase of monocline
(M/H2) and transformation (H2/H3) of the hexagonal phase to hexagonal phase；With the corresponding reduction peak of oxidation peak be respectively 3.70V, 3.97V and
4.20V left and right.
During the charge and discharge cycles of electrode material, when layered electrode material is changed from H2 to the structure of H3,
It can lead to the volume contraction of ternary material, this is the major reason of material capacity attenuation.
By Figure 12 it can also be seen that compared with sample exposure in air is made in comparative example 1, it is sudden and violent that sample is made in embodiment 1
Reveal aerial invertibity to make moderate progress.
During the cyclic voltammetry data of above-mentioned sample are listed in the table below 3,
3 cyclic voltammetry data of table
As shown in Table 3, main oxidation peak and main reduction peak potential differenceThe invertibity of material is represented, difference is smaller, reversible
Property is higher.
The testing impedance matched curve analysis of 8 sample of experimental example
This experimental example used sample is made for embodiment 1 and comparative example 1.
Testing impedance matched curve analysis is carried out to above-mentioned sample, as a result as shown in figure 13, wherein, the figure in the upper left corner is high
The enlarged drawing in frequency area.
As shown in Figure 13, the impedance diagram of two kinds of materials is all made of two circular arcs and straight line, the Europe of this and material
Nurse impedance, membrane impedance and load transfer impedance are corresponding.
Wherein, first circular arc corresponds to high frequency region, for the SEI membrane impedances that electrolyte is formed with electrode surface, second circle
Arc corresponds to intermediate frequency zone, is interfacial electrochemistry impedance, and line correspondences low frequency range is impedance caused by lithium ion solid-state diffusion.
The impedance data of two kinds of materials is fitted by Z-View softwares, embodiment 1 is made as can be seen from Figure 13
The smaller of sample is made in the SEI membrane impedance relative contrasts example 1 of sample high frequency region, and the interfacial electrochemistry impedance of intermediate frequency zone is higher than comparison
Example 1, low frequency range is close.
The impedance data of two kinds of materials is fitted by Z-View softwares, fitting data is as shown in table 4.
4 testing impedance fitting data of table
As shown in Table 4, when embodiment 1 is made sample and comparative example 1 sample exposure simultaneously is made in air, embodiment 1
Be made sample electrochemical impedance Rct have reduction, i.e. material polarizes smaller during charge and discharge cycles, chemical property compared with
Good, the test of impedance test results and charge and discharge cycles is consistent.
The present invention is described in detail above in association with specific embodiment and exemplary example, but these explanations are simultaneously
It is not considered as limiting the invention.It will be appreciated by those skilled in the art that without departing from the spirit and scope of the invention,
A variety of equivalencings, modification or improvement can be carried out to technical solution of the present invention and embodiments thereof, these each fall within the present invention
In the range of.Protection scope of the present invention is determined by the appended claims.
Claims (10)
1. a kind of anode material for lithium-ion batteries with water resistance, which is characterized in that the positive electrode includes nickelic anode
Material body and the silane coupling agent layer for being coated on its surface.
2. positive electrode according to claim 1, which is characterized in that
The chemical composition of nickelic positive electrode ontology is LiNixCoyMn1-x-yO2, wherein,
0.5≤x≤0.8,0.1≤y≤0.2.
3. positive electrode according to claim 1 or 2, which is characterized in that
Coating thickness is about 5~30nm, preferably 10~20nm, most preferably 15nm,
The silane coupling agent be epoxy group one type of silane coupling agent, preferably Silane coupling agent KH550, silane coupling agent KH560,
It is one or more in silane coupling agent KH570, silane coupling agent KH580.
4. the positive electrode according to one of claims 1 to 3, which is characterized in that the lithium ion with water resistance
Cell positive material,
Its pH is 11~12；And/or
Specific surface area is 0.4~0.5m2/g；And/or
Its tap density is 2.4g/cm3；And/or
Compacted density is 3.4~3.6g/cm3。
5. the positive electrode according to one of Claims 1-4, which is characterized in that
Can be that there are absorption peaks at 101.82eV in combination according to its X ray electron spectrum；
Its first discharge specific capacity discharged under 1C current densities is more than 155mAh/g；
Specific discharge capacity is more than 138mAh/g after 100 circle of cycle, and capacity retention ratio is more than 88%.
A kind of 6. method for preparing the anode material for lithium-ion batteries with water resistance, which is characterized in that the method includes
Following steps：
Step 1, silane coupling agent is configured to solution；
Step 2, nickelic positive electrode ontology is added in into silane coupler solution made from step 1, removes solvent；
Step 3, system made from step 2 is heat-treated, obtains the lithium ion cell positive material described in one of claim 1 to 5
Material.
7. according to the method described in claim 6, it is characterized in that, in step 1, prepare molten used in silane coupler solution
Agent is Small molecule organic solvents, preferably one or more in methanol, ethyl alcohol, acetone, dichloromethane, chloroform, more excellent
It is selected as methanol and/or ethyl alcohol, most preferably ethyl alcohol.
8. the method described according to claim 6 or 7, which is characterized in that in step 1, in silane coupler solution obtained, silicon
The volume ratio of alkane coupling agent and solvent is 1:(30~60), preferably 1:(40~55), most preferably 1:50.
9. the method according to one of claim 6 to 8, which is characterized in that in step 2,
The envelope-bulk to weight ratio of silane coupler solution and nickelic positive electrode ontology is 50mL:(3~8) g, preferably 50mL:(4
~6) g, most preferably 50mL:5g；And/or
In removing system during solvent, heating temperature is 50 DEG C~80 DEG C, preferably 55 DEG C~70 DEG C, more preferably 60 DEG C.
10. the method according to one of claim 6 to 9, which is characterized in that in step 3,
The temperature of heat treatment is 200 DEG C~400 DEG C, preferably 250 DEG C~350 DEG C, more preferably 300 DEG C；And/or
The time of heat treatment is 4~8 hours, preferably 5~7 hours, most preferably 6 hours.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111697223A (en) * | 2020-05-15 | 2020-09-22 | 浙江美达瑞新材料科技有限公司 | Surface modified lithium ion battery anode material and preparation method thereof |
| CN112820865A (en) * | 2021-02-05 | 2021-05-18 | 合肥国轩高科动力能源有限公司 | Preparation method of double-layer surface-coated high-nickel ternary single crystal positive electrode material |
| CN113952949A (en) * | 2021-09-14 | 2022-01-21 | 青岛创启迈沃环境科技有限公司 | Preparation method of hydrophobic normal-temperature decomposition ozone catalyst |
| CN114447302A (en) * | 2022-01-27 | 2022-05-06 | 中国科学院电工研究所 | Layered oxide/conductive agent composite material and preparation method and application thereof |
| WO2023088133A1 (en) * | 2021-11-18 | 2023-05-25 | 深圳市德方创域新能源科技有限公司 | Additive for supplementing lithium to positive electrode, and preparation method therefor and use thereof |
| WO2024087872A1 (en) * | 2022-10-24 | 2024-05-02 | 天津巴莫科技有限责任公司 | Ternary positive electrode material, and preparation method therefor and use thereof |
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| CN105576233A (en) * | 2016-03-03 | 2016-05-11 | 四川浩普瑞新能源材料股份有限公司 | Nickel base trinary positive electrode material and preparation method thereof |
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| CN105576233A (en) * | 2016-03-03 | 2016-05-11 | 四川浩普瑞新能源材料股份有限公司 | Nickel base trinary positive electrode material and preparation method thereof |
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| CN111697223A (en) * | 2020-05-15 | 2020-09-22 | 浙江美达瑞新材料科技有限公司 | Surface modified lithium ion battery anode material and preparation method thereof |
| CN112820865A (en) * | 2021-02-05 | 2021-05-18 | 合肥国轩高科动力能源有限公司 | Preparation method of double-layer surface-coated high-nickel ternary single crystal positive electrode material |
| CN113952949A (en) * | 2021-09-14 | 2022-01-21 | 青岛创启迈沃环境科技有限公司 | Preparation method of hydrophobic normal-temperature decomposition ozone catalyst |
| CN113952949B (en) * | 2021-09-14 | 2024-06-04 | 青岛创启迈沃环境科技有限公司 | Preparation method of hydrophobic normal-temperature decomposition ozone catalyst |
| WO2023088133A1 (en) * | 2021-11-18 | 2023-05-25 | 深圳市德方创域新能源科技有限公司 | Additive for supplementing lithium to positive electrode, and preparation method therefor and use thereof |
| CN114447302A (en) * | 2022-01-27 | 2022-05-06 | 中国科学院电工研究所 | Layered oxide/conductive agent composite material and preparation method and application thereof |
| CN114447302B (en) * | 2022-01-27 | 2024-02-13 | 中国科学院电工研究所 | Layered oxide/conductive agent composite material and preparation method and application thereof |
| WO2024087872A1 (en) * | 2022-10-24 | 2024-05-02 | 天津巴莫科技有限责任公司 | Ternary positive electrode material, and preparation method therefor and use thereof |
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