CN108767208A - Acid with strong oxidizing property, which handles structured surface, has the disordered structure anode material for lithium-ion batteries and preparation method thereof of high-valence state transition metal - Google Patents
Acid with strong oxidizing property, which handles structured surface, has the disordered structure anode material for lithium-ion batteries and preparation method thereof of high-valence state transition metal Download PDFInfo
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Abstract
The invention discloses the disordered structure anode material for lithium-ion batteries and preparation method thereof that a kind of acid with strong oxidizing property processing structured surface has high-valence state transition metal, using lithium ion anode material as raw material, it is handled in the acid of strong oxidizing property, forms the disordered structure superficial layer with high-valence state transition metal.The present invention has effectively handled the LiOH of material surface remnants, Li2CO3With free lithium metal, the pH value of material is reduced, while surface high-valence state transition metal easily makes Li+Quick deintercalation improves lithium ion transport efficiency, and the change of high-valence state transition metal photoinduced electron structure, so that it is generated the surface texture of three one-dimensional disorders, provides channel for lithium ion transport, improve lithium ion diffusion coefficient, improve the specific capacity of material, high rate performance and cyclical stability.And preparation method is simple by the present invention, at low cost, is suitble to large-scale industrial production.
Description
Technical field
The present invention relates to technical field of lithium ion, more particularly to a kind of acid with strong oxidizing property processing construction table
Face has the disordered structure anode material for lithium-ion batteries and preparation method thereof of high-valence state transition metal.
Background technology
Currently, with environmental pollution, the gradual aggravation of resource exhaustion, generation of the lithium ion battery as Green Chemistry power supply
Table has the advantages that energy density is high, good cycle, operating voltage is high, therefore of increased attention.
But since the market demand in power battery field is constantly increasing, people are close to the energy of lithium ion battery
The requirement of degree is also higher and higher, and as the positive electrode for the most important factor for determining lithium ion battery chemical property, it is existing
The discharge capacity of positive electrode, cyclical stability, high rate performance etc. still cannot be satisfied the commercialized market demand, therefore improve lithium
The energy density of ion battery positive electrode and the popular problem that capacity density is still each side scholar research.
Now, the method that people commonly improve anode material for lithium-ion batteries energy density mainly has doping, cladding etc.；
Doping is mainly added some metallic elements and substitutes transition metal therein, and the lattice structure of stabilizing material avoids
Li/Ni mixings and transition metal in charge and discharge process are dissolved by HF, however the addition of some metals can not participate in electrochemistry
Redox reaction in the process cannot provide capacity, reduce the capacity of material；
Similar, oxide coated, fluoride and phosphate etc. can be to avoid on the surface of anode material for lithium-ion batteries
With electrolyte side reaction occurs for electrode material in cyclic process, improves the cycle performance of material, but covering material is mostly insulation
Body or semiconductor, to Li in material+Transmission plays inhibition, is unfavorable for improving the high rate performance of material.
In conclusion a kind of high performance anode material for lithium-ion batteries of research and development, and provide a kind of relatively simple lithium from
The problem of sub- cell positive material preparation method is those skilled in the art's urgent need to resolve.
Invention content
In view of this, it is an object of the present invention to provide a kind of high performance anode material for lithium-ion batteries, tool
Body is that acid with strong oxidizing property handles disordered structure anode material for lithium-ion batteries of the structured surface with high-valence state transition metal.
To achieve the goals above, the present invention adopts the following technical scheme that：
A kind of acid with strong oxidizing property processing structured surface has the disordered structure lithium ion cell positive of high-valence state transition metal
Material, including：Anode material for lithium-ion batteries and disordered structure superficial layer with high-valence state；
The thickness of the disordered structure superficial layer with high-valence state metal is 3-10nm.
Preferably, the anode material for lithium-ion batteries is manganese-based anode material LiMnxM1-xO2,LiMnxM1-xPO4,
LiMnxM1-xO4And yLi2MnO3·(1-y)LiMnxM1-xO2One or more of mixture, wherein 0<x≤ 1,0<Y≤1,
M is Ni, Co, Fe, Ti, Zn, Ba, Nb, Cu, Mo, Ba, Ru, Ir, Sr, Cr, Y, Ga, K, Mg, V, one or more of Zr.
By using above-mentioned technical proposal, the beneficial effects of the present invention are：
It is 3 that the present invention, which has the disordered structure lithium battery anode material lithium ionic diffusion coefficient of high-valence state transition metal,
×10-11cm2/ s, in contrast to the 0.8 × 10 of original anode material for lithium-ion batteries-12cm2/ s is enhanced；Comparison is just
The electrochemical property test that the lithium-ion button battery of pole material preparation carries out, the disordered structure lithium with high-valence state transition metal
Specific discharge capacity of the ion battery positive electrode under different current densities is higher than original positive electrode, in 30mA/g
Specific discharge capacity be 250-300mA h/g, still have 150-200mAh/g under 500mA/g current densities, the lithium ion battery
Capacity retention ratio is 92% or more after being recycled 100 times under 300mA/g current densities.
It is another object of the present invention to provide a kind of acid with strong oxidizing property processing structured surfaces to have high-valence state transition gold
The preparation method of the disordered structure anode material for lithium-ion batteries of category.
To achieve the goals above, technical scheme is as follows：
A kind of acid with strong oxidizing property processing structured surface has the disordered structure lithium ion cell positive of high-valence state transition metal
The preparation method of material, includes the following steps：
Step 1：Appropriate acid with strong oxidizing property is added to the water, stirring is configured to strong oxidizing property acid solution to being uniformly mixed；
Step 2：Anode material for lithium-ion batteries is added in the solution of step 1, stirring makes lithium ion cell positive material
Material surface transition metal ion is substantially oxidized, and is filtered, and is washed, dry；
Step 3：Material after step 2 is dried is sintered, and obtaining surface has high-valence state transition metal
Anode material for lithium-ion batteries.
By using above-mentioned technical proposal, beneficial effects of the present invention are as follows：
By the way that suitable acid with strong oxidizing property to be added to the water, magnetic agitation is configured to certain dense the present invention to being uniformly mixed
The strong oxidizing property acid solution of degree, after anode material for lithium-ion batteries is added in prepared solution, magnetic agitation certain time
So that anode material for lithium-ion batteries surface transition metal ion is substantially oxidized, filter, washs, it is dry, and by the material after drying
Material is sintered in an inert atmosphere, and obtaining surface has the disordered structure lithium ion cell positive of high-valence state transition metal
Material；Since material will be in the state of moment charge balance in charge and discharge process, so that the Li in material+It is more prone to de-
Go out, improves the Li of material+Efficiency of transmission, while surface transition metal is oxidized to higher valent state can make its electronic structure
It changes, inducement structure is changed from two-dimensional layer to three disordered structures, and three disordered structures can carry for lithium ion transport
For channel, the lithium ion diffusion coefficient of material is improved, and then promote the high rate performance of material；In addition acid processing can be with neutralization materials
The LiOH of surface residual reduces the pH of material, improves the discharge capacity of material, is played an important role to industrialized production.
Preferably, the acid with strong oxidizing property used in the step 1 is polyacid compound, specially perchloric acid, hyperbromic acid,
Periodic acid, hypochlorous acid, persulfuric acid, dichromic acid, one kind in hydrogen peroxide.
By using above-mentioned optimal technical scheme, the beneficial effects of the present invention are：
The existing strong oxidizing property of polyacid compound that the present invention uses has acidity again, and the mistake of material surface can be made after processing
The chemical valence for crossing metal has a degree of promotion, since material will be in the state of charge balance, so that the Li in material+
It is more prone to deviate from, improves the Li of material+Efficiency of transmission；Meanwhile the LiOH of acid solution meeting neutralization materials surface residual,
Li2CO3Deng reducing the pH value of material surface, reduce susceptibility and free lithium content of the material to water, improve the specific volume of material
Amount.
Preferably, a concentration of 0.1-2g/L of the strong oxidizing property acid solution configured in the step 1.
Preferably, the mass ratio of the anode material for lithium-ion batteries and acid with strong oxidizing property that are added in the step 2 is 1-
100:1。
Preferably, the specific process parameter in the step 2 is as follows：Mixing time is 0.5-2h, and dry temperature is
50-120 DEG C, drying time 8-12h.
Preferably, the sintering temperature in the step 3 is 400-600 DEG C, sintering time 2-6h, heating rate 1-
10℃/min。
Preferably, the atmosphere of sintering processes is nitrogen atmosphere, argon gas atmosphere, helium atmosphere, oxygen gas in the step 3
One or more of atmosphere.
It can be seen via above technical scheme that the present disclosure provides a kind of acid with strong oxidizing property processing structured surfaces to have
The disordered structure anode material for lithium-ion batteries of high-valence state transition metal, and preparation method is disclosed, compared with prior art,
Beneficial effects of the present invention are as follows：
1) present invention is using the acid processing anode material for lithium-ion batteries with strong oxidizing property, if material surface pH is excessive,
Can be more sensitive to moisture, wherein transition metal is easily corroded by the HF that electrolyte reaction generates.The present invention using acid processing lithium from
Sub- cell positive material surface, neutralizes the LiOH of its surface residual, Li2CO3Deng reducing the pH value of material, make material to the quick of water
The lithium content that sensitivity and surface are dissociated reduces, and is conducive to improve the specific capacity and cyclical stability of material；
2) present invention uses the acid processing anode material for lithium-ion batteries with strong oxidizing property so that surface transition metallizes
Conjunction valence increases, since material will be in the state of moment charge balance in charge and discharge process, so that the Li in material+More hold
Easily abjection, improves the Li of material+Efficiency of transmission；Simultaneously induce its electronic structure to change, material from two-dimensional layered structure to
Three-dimensional disordered structure transformation provides channel for ion transmission, improves the lithium ion diffusion coefficient of material, and then promotes times of material
Rate performance；
3) preparation method of the invention is simple and significant effect, of low cost, instrument and environmental requirement needed for preparation process
It is not high, it is suitble to large-scale industrial production.
Description of the drawings
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technology description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this
The embodiment of invention for those of ordinary skill in the art without creative efforts, can also basis
The attached drawing of offer obtains other attached drawings.
Fig. 1 is the SEM figures of lithium-rich anode material in embodiment 1；
Fig. 2 is the SEM figures of the disordered structure anode material for lithium-ion batteries with high-valence state transition metal in embodiment 1；
Fig. 3 is the XPS test charts tested in embodiment 1；
Fig. 4 is the curve of double curvature figure in embodiment 1；
Fig. 5 is the cycle performance curve graph under 300mA/g current densities in embodiment 1.
Specific implementation mode
Following will be combined with the drawings in the embodiments of the present invention, and technical solution in the embodiment of the present invention carries out clear, complete
Site preparation describes, it is clear that described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.It is based on
Embodiment in the present invention, it is obtained by those of ordinary skill in the art without making creative efforts every other
Embodiment shall fall within the protection scope of the present invention.
The invention discloses the disordered structure lithiums that a kind of acid with strong oxidizing property processing structured surface has high-valence state transition metal
Ion battery positive electrode, including：Anode material for lithium-ion batteries and disordered structure superficial layer with high-valence state have high price
The disordered structure superficial layer of state metal is 3-10nm.
In order to further realize technical scheme of the present invention, anode material for lithium-ion batteries is manganese-based anode material
LiMnxM1-xO2,LiMnxM1-xPO4,LiMnxM1-xO4And yLi2MnO3·(1-y)LiMnxM1-xO2One or more of mixing
Object, wherein 0<x≤1,0<Y≤1, M Ni, Co, Fe, Ti, Zn, Ba, Nb, Cu, Mo, Ba, Ru, Ir, Sr, Cr, Y, Ga, K, Mg,
One or more of V, Zr.
The invention discloses the disordered structure lithiums that a kind of acid with strong oxidizing property processing structured surface has high-valence state transition metal
The preparation method of ion battery positive electrode, includes the following steps：
Step 1：Appropriate acid with strong oxidizing property is added to the water, stirring is configured to strong oxidizing property acid solution to being uniformly mixed,
A concentration of 0.1-2g/L of strong oxidizing property acid solution；
Step 2：Anode material for lithium-ion batteries is added in the solution of step 1, the lithium ion cell positive material of addition
Material and the mass ratio of acid with strong oxidizing property are 1-100:1, stirring makes anode material for lithium-ion batteries surface transition metal ion be filled
Divide oxidation, filter, wash, dry, mixing time 0.5-2h, dry temperature is 50-120 DEG C, drying time 8-12h；
Step 3：Material after step 2 is dried is sintered, and sintering temperature is 400-600 DEG C, sintering time
For 2-6h, heating rate is 1-10 DEG C/min, and then obtaining surface has the lithium ion cell positive material of high-valence state transition metal
Material.
In order to further realize technical scheme of the present invention, the acid with strong oxidizing property used in step 1 for polyacid compound,
Specially perchloric acid, hyperbromic acid, periodic acid, hypochlorous acid, persulfuric acid, dichromic acid, one kind in hydrogen peroxide, can also be silicon tungsten
Acid.
In order to further realize technical scheme of the present invention, the atmosphere during sintering processes in step 3 is nitrogen gas
Atmosphere, argon gas atmosphere, helium atmosphere, one or more of oxygen atmosphere.
The present invention is discussed further below in conjunction with specific embodiment.
Embodiment 1：
It weighs 0.005g silico-tungstic acids to be placed in 100mL beakers, measuring 30mL water with graduated cylinder is added thereto, magnetic agitation
30min, then weigh 0.495g lithium-rich anode materials Li1.2Mn0.54Ni0.13Co0.13O2It is added in beaker, continues to stir 30min, so
The suspension in beaker is filtered afterwards, cleaning the material three times, obtained with ultra-pure water is placed in vacuum drying chamber the drying at 80 DEG C
10h；Obtained powder is put into magnetic boat and is warming up to 600 DEG C in Muffle furnace with the heating rate of 2 DEG C/min, and keeps 2h,
Temperature fall afterwards, surface, which is made, has the disordered structure anode material for lithium-ion batteries of high-valence state transition metal.
Embodiment 2：
It weighs 0.003g perchloric acid to be placed in 100mL beakers, measuring 30mL water with graduated cylinder is added thereto, magnetic agitation
30min, then weigh 0.003g anode material for lithium-ion batteries LiNi0.8Co0.1Mn0.1O2It is added in beaker, continues to stir 1h, so
The suspension in beaker is filtered afterwards, cleaning the material three times, obtained with ultra-pure water is placed in vacuum drying chamber the drying at 50 DEG C
8h；Obtained powder is put into magnetic boat and is warming up to 400 DEG C in Muffle furnace with the heating rate of 1 DEG C/min, and keeps 3h, after
Temperature fall, surface, which is made, has the disordered structure anode material for lithium-ion batteries of high-valence state transition metal.
Embodiment 3：
It weighs 0.06g hydrogen peroxide to be placed in 100mL beakers, measuring 30mL water with graduated cylinder is added thereto, magnetic agitation
30min, then weigh 2.88g anode material for lithium-ion batteries LiMnPO4It is added in beaker, continues to stir 2h, it then will be in beaker
Suspension filter, with ultra-pure water clean the material three times, obtained be placed in vacuum drying chamber at 120 DEG C dry 12h；It will obtain
Powder be put into magnetic boat and be warming up to 500 DEG C in Muffle furnace with the heating rate of 10 DEG C/min, and keep 6h, afterwards drop naturally
Temperature, surface, which is made, has the disordered structure anode material for lithium-ion batteries of high-valence state transition metal.
Experiment one：
There is the disordered structure lithium ion battery of high-valence state transition metal just using the surface that above-described embodiment 1 is prepared
Pole material carries out further judgement experiment, proves that the surface that the present invention is prepared has the nothing of high-valence state transition metal with this
Sequence structure anode material for lithium-ion batteries has excellent performance.
In the following, will be further detailed in conjunction with Figure of description.
As shown in FIG. 1, FIG. 1 is the SEM figures of lithium-rich anode material prepared by embodiment 1.
As seen from Figure 1, the lithium-rich anode material prepared is spherical structure, and shape is not very regular, and size is at 8 μm
Left and right, porous surface are rougher；Surface has the SEM figures of the disordered structure lithium-rich anode material of high-valence state transition metal simultaneously.
As shown in Fig. 2, Fig. 2 is the disordered structure lithium ion cell positive material with high-valence state transition metal in embodiment 1
The SEM of material schemes.
As seen from Figure 2, it is still spherical structure that surface, which has the rich lithium material of the disordered structure of high-valence state transition metal,
Surface is smooth before relatively coating, and shows still have compared with concrete dynamic modulus.
Next, rich lithium material and original rich lithium to disordered structure of the surface with high-valence state transition metal of preparation are just
Pole material Li1.2Mn0.54Ni0.13Co0.13O2Carry out XPS tests, test results are shown in figure 3, wherein 1 be lithium-rich anode material, 2
For the disordered structure anode material for lithium-ion batteries with high-valence state transition metal.
By the peaks Fig. 3 Mn2p it is found that the 2p of original rich lithium material3/2Peak position is in 642.8eV, and 2p3/2With 2p1/2's
It is 11.5eV in conjunction with energy difference, the surface of preparation has the peaks 2p of the Mn of the rich lithium material of the disordered structure of high-valence state transition metal
The peak of more original richness lithium material combines energy direction to deviate to height, shows that the chemical valence of surface Mn in material is increasing, illustrates the party
Method prepares the lithium-rich anode material of disordered structure of the surface with high-valence state transition metal；
Surface prepared by embodiment 1 has the disordered structure lithium-rich anode material and lithium-rich anode of high-valence state transition metal
Material (Li1.2Mn0.54Ni0.13Co0.13O2) carried out with lithium piece, polyolefin porous separator and commercial electrolyte liquid composition lithium ion battery
Electrochemical property test；Test results are shown in figure 4, wherein 1 is lithium-rich anode material, 2 is with high-valence state transition metal
Disordered structure anode material for lithium-ion batteries.
As shown in Figure 4, surface has electricity of the lithium-rich anode material in 30 mA/g of the disordered structure of high-valence state transition metal
Specific discharge capacity is 260.37mAh/g under current density, and the specific discharge capacity under 500mA/g current densities is 158.38mAh/g,
And lithium-rich anode material (Li1.2Mn0.54Ni0.13Co0.13O2) first discharge specific capacity is under the current density of 30mA/g
229.36mAh/g, the specific discharge capacity under 500mA/g current densities are 124.78mAh/g.
Test surfaces have the lithium-rich anode material of the disordered structure of high-valence state transition metal and original rich lithium material
(Li1.2Mn0.54Ni0.13Co0.13O2) composition cycle performance curve of the lithium ion battery at 300mA/g, test result such as Fig. 5
Shown, wherein 1 is lithium-rich anode material, 2 have the disordered structure lithium ion cell positive material of high-valence state transition metal for surface
Material.
As shown in Figure 5, surface of the present invention has the cycle of the lithium-rich anode material of the disordered structure of high-valence state transition metal
Performance is also more excellent, and after recycling 100 times, capacity retention ratio is up to conservation rate 94%.
In conclusion the present invention solves existing anode material for lithium-ion batteries since conductivity is low, two-dimensional structure is not
It is easy to Li+Transmission, the problems such as surface pH value is higher and caused by material discharging specific capacity it is low, the problems such as high rate performance is poor, provide
A kind of acid with strong oxidizing property processing structured surface have high-valence state transition metal disordered structure anode material for lithium-ion batteries and
Preparation method.
Each embodiment is described by the way of progressive in this specification, the highlights of each of the examples are with other
The difference of embodiment, just to refer each other for identical similar portion between each embodiment.For device disclosed in embodiment
For, since it is corresponded to the methods disclosed in the examples, so description is fairly simple, related place is said referring to method part
It is bright.
The foregoing description of the disclosed embodiments enables those skilled in the art to implement or use the present invention.
Various modifications to these embodiments will be apparent to those skilled in the art, as defined herein
General Principle can be realized in other embodiments without departing from the spirit or scope of the present invention.Therefore, of the invention
It is not intended to be limited to the embodiments shown herein, and is to fit to and the principles and novel features disclosed herein phase one
The widest range caused.
Claims (9)
1. a kind of acid with strong oxidizing property processing structured surface has the disordered structure lithium ion cell positive material of high-valence state transition metal
Material, which is characterized in that including：Anode material for lithium-ion batteries and disordered structure superficial layer with high-valence state；
The thickness of the disordered structure superficial layer with high-valence state metal is 3-10nm.
2. a kind of acid with strong oxidizing property processing structured surface according to claim 1 has the unordered knot of high-valence state transition metal
Structure anode material for lithium-ion batteries, which is characterized in that the anode material for lithium-ion batteries is manganese-based anode material LiMnxM1- xO2,LiMnxM1-xPO4,LiMnxM1-xO4And yLi2MnO3·(1-y)LiMnxM1-xO2One or more of mixture, wherein
0<x≤1,0<In y≤1, M Ni, Co, Fe, Ti, Zn, Ba, Nb, Cu, Mo, Ba, Ru, Ir, Sr, Cr, Y, Ga, K, Mg, V, Zr
It is one or more of.
3. a kind of acid with strong oxidizing property processing structured surface has the disordered structure lithium ion cell positive material of high-valence state transition metal
The preparation method of material, which is characterized in that include the following steps：
Step 1：Appropriate acid with strong oxidizing property is added to the water, stirring is configured to strong oxidizing property acid solution to being uniformly mixed；
Step 2：Anode material for lithium-ion batteries is added in the solution of step 1, stirring makes anode material for lithium-ion batteries table
Face transition metal ions is substantially oxidized, and is filtered, and is washed, dry；
Step 3：Material after step 2 is dried is sintered, obtain surface with high-valence state transition metal lithium from
Sub- cell positive material.
4. a kind of acid with strong oxidizing property processing structured surface according to claim 3 has the unordered knot of high-valence state transition metal
The preparation method of structure anode material for lithium-ion batteries, which is characterized in that the acid with strong oxidizing property used in the step 1 is polyacid
Compound, specially perchloric acid, hyperbromic acid, periodic acid, hypochlorous acid, persulfuric acid, dichromic acid, one kind in hydrogen peroxide.
5. a kind of acid with strong oxidizing property processing structured surface according to claim 3 has the unordered knot of high-valence state transition metal
The preparation method of structure anode material for lithium-ion batteries, which is characterized in that the acid with strong oxidizing property configured in the step 1 is molten
A concentration of 0.1-2g/L of liquid.
6. a kind of acid with strong oxidizing property processing structured surface according to claim 3 has the unordered knot of high-valence state transition metal
The preparation method of structure anode material for lithium-ion batteries, which is characterized in that the lithium ion cell positive material being added in the step 2
Material and the mass ratio of acid with strong oxidizing property are 1-100:1.
7. a kind of acid with strong oxidizing property processing structured surface according to claim 3 has the unordered knot of high-valence state transition metal
The preparation method of structure anode material for lithium-ion batteries, which is characterized in that the specific process parameter in the step 2 is as follows：Stirring
Time is 0.5-2h, and dry temperature is 50-120 DEG C, drying time 8-12h.
8. a kind of acid with strong oxidizing property processing structured surface according to claim 3 has the unordered knot of high-valence state transition metal
The preparation method of structure anode material for lithium-ion batteries, which is characterized in that the sintering temperature in the step 3 is 400-600 DEG C,
Sintering time is 2-6h, and heating rate is 1-10 DEG C/min.
9. a kind of acid with strong oxidizing property processing structured surface according to claim 3 has the unordered knot of high-valence state transition metal
The preparation method of structure anode material for lithium-ion batteries, which is characterized in that the atmosphere in sintering processes in the step 3 is nitrogen
Gas atmosphere, argon gas atmosphere, helium atmosphere, one or more of oxygen atmosphere.
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