CN108767208B - Disordered-structure lithium ion battery anode material with high-valence transition metal on surface of strong-oxidizing-acid-treatment structure and preparation method of disordered-structure lithium ion battery anode material - Google Patents
Disordered-structure lithium ion battery anode material with high-valence transition metal on surface of strong-oxidizing-acid-treatment structure and preparation method of disordered-structure lithium ion battery anode material Download PDFInfo
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Abstract
The invention discloses a disordered structure lithium ion battery anode material with high-valence transition metal on the surface of a strong oxidizing acid treatment structure and a preparation method thereof. The invention effectively treats residual LiOH and Li on the surface of the material2CO3And free metallic lithium, the pH value of the material is reduced, and meanwhile, Li is easy to be caused by high-valence transition metal on the surface+The lithium ion battery has the advantages that the lithium ion battery is rapidly de-intercalated, the transmission efficiency of lithium ions is improved, the high-valence transition metal induces the change of an electronic structure, so that the electronic structure generates a three-dimensional disordered surface structure, a channel is provided for the transmission of the lithium ions, the diffusion coefficient of the lithium ions is improved, and the specific capacity, the rate capability and the cycling stability of the material are improved. The preparation method is simple and feasible, has low cost and is suitable for large-scale industrial production.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a disordered structure lithium ion battery cathode material with a high-valence transition metal on the surface of a strong-oxidizing acid treatment structure and a preparation method thereof.
Background
At present, along with environmental pollution and gradual increase of resource exhaustion, lithium ion batteries, as a representative of green chemical power sources, have the advantages of high energy density, good cycle performance, high working voltage and the like, and therefore, are receiving more and more attention.
However, as market demands in the field of power batteries are continuously increased, people have higher and higher requirements on energy density of lithium ion batteries, and the discharge capacity, the cycle stability, the rate capability and the like of the conventional positive electrode material, which are the most important factors for determining the electrochemical performance of the lithium ion batteries, still cannot meet the commercial market demands, so that the improvement of the energy density and the capacity density of the positive electrode material of the lithium ion batteries is still a popular problem for researches of various researchers.
At present, the common methods for improving the energy density of the anode material of the lithium ion battery mainly comprise doping, cladding and the like;
doping is mainly to add some metal elements to replace transition metals in the materials, stabilize the lattice structure of the materials, and avoid Li/Ni mixed discharge and the dissolution of the transition metals by HF in the charge and discharge processes, however, the addition of some metals cannot participate in the redox reaction in the electrochemical process, cannot provide capacity, and reduces the capacity of the materials;
similarly, the surface of the anode material of the lithium ion battery is coated with oxides, fluorides, phosphates and the like, so that the side reaction between the electrode material and electrolyte in the circulation process can be avoided, the circulation performance of the material is improved,however, the cladding material is mostly an insulator or a semiconductor, and Li in the cladding material+The transmission plays a role in blocking, and the rate capability of the material is not improved.
In summary, it is an urgent need to solve the problems in the art to develop a high-performance lithium ion battery cathode material and provide a simpler preparation method of the lithium ion battery cathode material.
Disclosure of Invention
In view of the above, an object of the present invention is to provide a high-performance lithium ion battery cathode material, specifically, a lithium ion battery cathode material with a disordered structure having a high-valence transition metal on the surface of a strong-oxidizing acid-treated structure.
In order to achieve the purpose, the invention adopts the following technical scheme:
a disordered structure lithium ion battery anode material with high-valence transition metal on the surface of a strong-oxidizing acid treatment structure comprises: the lithium ion battery comprises a lithium ion battery anode material and a disordered structure surface layer with a high valence state;
the thickness of the disordered structure surface layer of the metal with the high valence state is 3-10 nm.
Preferably, the lithium ion battery positive electrode material is a manganese-based positive electrode material LiMnxM1-xO2,LiMnxM1-xPO4, LiMnxM1-xO4And yLi2MnO3·(1-y)LiMnxM1-xO2Wherein 0 is one or a mixture of several of<x≤ 1,0<Y is less than or equal to 1, M is one or more of Ni, Co, Fe, Ti, Zn, Ba, Nb, Cu, Mo, Ba, Ru, Ir, Sr, Cr, Y, Ga, K, Mg, V and Zr.
By adopting the technical scheme, the invention has the beneficial effects that:
the lithium ion diffusion coefficient of the disordered structure lithium ion battery anode material with high-valence transition metal is 3 multiplied by 10-11cm2S, 0.8X 10 compared with the original lithium ion battery anode material-12cm2The/s is greatly improved; comparing with the lithium-ion button cell prepared by positive electrode materialAccording to electrochemical performance tests, the discharge specific capacity of the lithium ion battery anode material with the disordered structure of the high-valence transition metal under different current densities is higher than that of the original anode material, the discharge specific capacity is 250-300mA h/g at 30mA/g, the discharge specific capacity is still 150-200mAh/g at 500mA/g, and the capacity retention rate of the lithium ion battery is more than 92% after the lithium ion battery is cycled for 100 times under 300mA/g current density.
The invention also aims to provide a preparation method of the disordered-structure lithium ion battery positive electrode material with the high-valence transition metal on the surface of the strong-oxidizing acid treatment structure.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a preparation method of a disordered-structure lithium ion battery anode material with high-valence transition metal on the surface of a strong-oxidizing-property acid treatment structure comprises the following steps:
the method comprises the following steps: adding a proper amount of strong oxidizing acid into water, stirring until the mixture is uniformly mixed, and preparing a strong oxidizing acid solution;
step two: adding the lithium ion battery anode material into the solution obtained in the first step, stirring to fully oxidize transition metal ions on the surface of the lithium ion battery anode material, filtering, washing and drying;
step three: and sintering the material dried in the second step to obtain the lithium ion battery anode material with high-valence transition metal on the surface.
By adopting the technical scheme, the invention has the following beneficial effects:
adding a proper amount of strong oxidizing acid into water, magnetically stirring until the strong oxidizing acid and the strong oxidizing acid are uniformly mixed to prepare a strong oxidizing acid solution with a certain concentration, then adding a lithium ion battery anode material into the prepared solution, magnetically stirring for a certain time to fully oxidize transition metal ions on the surface of the lithium ion battery anode material, filtering, washing and drying, and sintering the dried material in an inert atmosphere to obtain the disordered lithium ion battery anode material with the surface having high-valence transition metal; during the charging and discharging process, the material is in a state of charge balance at any moment, so thatLi in the material+Is easier to be removed, and improves the Li of the material+The transmission efficiency is improved, meanwhile, the electronic structure of the surface transition metal is changed by oxidizing the surface transition metal into a higher valence state, the induced structure is changed from a two-dimensional layer structure to a three-dimensional disordered structure, and the three-dimensional disordered structure can provide a channel for lithium ion transmission, improve the lithium ion diffusion coefficient of the material and further improve the multiplying power performance of the material; in addition, the acid treatment can neutralize residual LiOH on the surface of the material, reduce the pH value of the material, improve the discharge capacity of the material and play an important role in industrial production.
Preferably, the strongly oxidizing acid used in the first step is a polyacid compound, specifically one of perchloric acid, perbromic acid, periodic acid, hypochlorous acid, persulfuric acid, dichromic acid, and hydrogen peroxide.
By adopting the preferable technical scheme, the invention has the beneficial effects that:
the polyacid compound adopted by the invention has strong oxidizing property and acidity, the valence of the transition metal on the surface of the material can be improved to a certain degree after treatment, and Li in the material is in a charge balance state+Is easier to be removed, and improves the Li of the material+Transmission efficiency; meanwhile, the acid solution can neutralize residual LiOH and Li on the surface of the material2CO3And the pH value of the surface of the material is reduced, the sensitivity of the material to water and the content of free lithium are reduced, and the specific capacity of the material is improved.
Preferably, the concentration of the strong oxidizing acid solution prepared in the first step is 0.1-2 g/L.
Preferably, the mass ratio of the lithium ion battery positive electrode material added in the second step to the strong oxidizing acid is 1-100: 1.
Preferably, the specific process parameters in the second step are as follows: stirring for 0.5-2h, drying at 50-120 deg.C for 8-12 h.
Preferably, the sintering temperature in the third step is 400-.
Preferably, the atmosphere of the sintering treatment in the third step is one or more of a nitrogen atmosphere, an argon atmosphere, a helium atmosphere and an oxygen atmosphere.
According to the technical scheme, the invention discloses a disordered structure lithium ion battery anode material with a high-valence transition metal on the surface of a strong oxidizing acid treatment structure, and discloses a preparation method thereof, and compared with the prior art, the disordered structure lithium ion battery anode material has the following beneficial effects:
1) the invention uses acid with strong oxidizing property to treat the lithium ion battery anode material, if the pH value of the surface of the material is too large, the material is sensitive to moisture, and transition metal is easy to be corroded by HF generated by the reaction of electrolyte. The invention uses acid to treat the surface of the anode material of the lithium ion battery and neutralize the residual LiOH and Li on the surface2CO3The pH value of the material is reduced, so that the sensitivity of the material to water and the content of free lithium on the surface are reduced, and the specific capacity and the cycling stability of the material are improved;
2) the invention uses acid with strong oxidizing property to treat the lithium ion battery anode material, so that the valence of the transition metal on the surface is increased, and Li in the material is in a state of charge balance at any moment in the charge-discharge process+Is easier to be removed, and improves the Li of the material+Transmission efficiency; meanwhile, the electronic structure of the material is induced to change, the material is changed from a two-dimensional layered structure to a three-dimensional disordered structure, a channel is provided for ion transmission, the lithium ion diffusion coefficient of the material is improved, and the multiplying power performance of the material is further improved;
3) the preparation method is simple, has obvious effect, low cost and low requirements on instruments and environment required in the preparation process, and is suitable for large-scale industrial production.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the provided drawings without creative efforts.
FIG. 1 is an SEM image of a lithium-rich cathode material of example 1;
fig. 2 is an SEM image of the disordered structure lithium ion battery positive electrode material having a high-valence transition metal in example 1;
FIG. 3 is an XPS test chart measured in example 1;
FIG. 4 is a graph showing magnification in example 1;
FIG. 5 is a graph of the cycling performance at a current density of 300mA/g in example 1.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention discloses a disordered structure lithium ion battery anode material with high-valence transition metal on the surface of a strong oxidizing acid treatment structure, which comprises the following components: the lithium ion battery anode material and the disordered structure surface layer with high valence state, the disordered structure surface layer with high valence state metal is 3-10 nm.
In order to further realize the technical scheme of the invention, the anode material of the lithium ion battery is a manganese-based anode material LiMnxM1-xO2,LiMnxM1-xPO4,LiMnxM1-xO4And yLi2MnO3·(1-y)LiMnxM1-xO2Wherein 0 is one or a mixture of several of<x≤1,0<Y is less than or equal to 1, M is one or more of Ni, Co, Fe, Ti, Zn, Ba, Nb, Cu, Mo, Ba, Ru, Ir, Sr, Cr, Y, Ga, K, Mg, V and Zr.
The invention discloses a preparation method of a disordered structure lithium ion battery anode material with high-valence transition metal on the surface of a strong-oxidizing acid treatment structure, which comprises the following steps:
the method comprises the following steps: adding a proper amount of strong oxidizing acid into water, stirring until the mixture is uniformly mixed to prepare a strong oxidizing acid solution, wherein the concentration of the strong oxidizing acid solution is 0.1-2 g/L;
step two: adding a lithium ion battery anode material into the solution obtained in the step one, wherein the mass ratio of the added lithium ion battery anode material to the strong oxidizing acid is 1-100:1, stirring to fully oxidize transition metal ions on the surface of the lithium ion battery anode material, filtering, washing, and drying, wherein the stirring time is 0.5-2h, the drying temperature is 50-120 ℃, and the drying time is 8-12 h;
step three: and (3) sintering the material dried in the second step at the sintering temperature of 400-.
In order to further realize the technical scheme of the invention, the strong oxidizing acid adopted in the step one is a polyacid compound, specifically one of perchloric acid, perbromic acid, periodic acid, hypochlorous acid, persulfuric acid, dichromic acid and hydrogen peroxide, and can also be silicotungstic acid.
In order to further realize the technical scheme of the invention, the atmosphere in the sintering treatment process in the step three is one or more of nitrogen atmosphere, argon atmosphere, helium atmosphere and oxygen atmosphere.
The present invention will be described in further detail with reference to specific examples.
Example 1:
weighing 0.005g of silicotungstic acid in a 100mL beaker, weighing 30mL of water in a measuring cylinder, adding the water, magnetically stirring for 30min, and weighing 0.495g of Li-rich cathode material1.2Mn0.54Ni0.13Co0.13O2Adding into a beaker, continuously stirring for 30min, then carrying out suction filtration on the suspension in the beaker, washing with ultrapure water for three times, and drying the obtained material in a vacuum drying oven at 80 ℃ for 10 h; and putting the obtained powder into a magnetic boat, heating to 600 ℃ in a muffle furnace at the heating rate of 2 ℃/min, keeping for 2h, and then naturally cooling to prepare the disordered-structure lithium ion battery anode material with the surface provided with the high-valence transition metal.
Example 2:
weighing 0.003g of perchloric acid in a 100mL beaker, weighing 30mL of water in a measuring cylinder, adding the water, magnetically stirring for 30min, and weighing 0.003g of LiNi which is a positive electrode material of a lithium ion battery0.8Co0.1Mn0.1O2Adding into a beaker, continuously stirring for 1h, then carrying out suction filtration on suspension in the beaker, washing with ultrapure water for three times, and drying the obtained material in a vacuum drying oven at 50 ℃ for 8 h; and putting the obtained powder into a magnetic boat, heating to 400 ℃ in a muffle furnace at the heating rate of 1 ℃/min, keeping for 3h, and then naturally cooling to prepare the lithium ion battery anode material with the disordered structure of the high-valence transition metal on the surface.
Example 3:
weighing 0.06g of hydrogen peroxide in a 100mL beaker, weighing 30mL of water in a measuring cylinder, adding the water, magnetically stirring for 30min, and weighing 2.88g of lithium ion battery anode material LiMnPO4Adding into a beaker, continuously stirring for 2h, then carrying out suction filtration on the suspension in the beaker, washing with ultrapure water for three times, and drying the obtained material in a vacuum drying oven at 120 ℃ for 12 h; and putting the obtained powder into a magnetic boat, heating to 500 ℃ in a muffle furnace at a heating rate of 10 ℃/min, keeping for 6 hours, and then naturally cooling to prepare the lithium ion battery anode material with the disordered structure of the high-valence transition metal on the surface.
Experiment one:
the lithium ion battery cathode material with the disordered structure and the high-valence transition metal on the surface, which is prepared in the embodiment 1, is used for further judgment experiments, so that the lithium ion battery cathode material with the disordered structure and the high-valence transition metal on the surface, which is prepared in the invention, has excellent performance.
The following will be further described with reference to the drawings of the specification.
As shown in fig. 1, fig. 1 is an SEM image of the lithium-rich cathode material prepared in example 1.
As can be seen from FIG. 1, the prepared lithium-rich cathode material has a spherical structure, is not very regular in shape, has a size of about 8 μm, and is porous and rough in surface; and meanwhile, the SEM image of the disordered-structure lithium-rich cathode material with the high-valence transition metal on the surface.
As shown in fig. 2, fig. 2 is an SEM image of the disordered structure lithium ion battery positive electrode material having a high valence transition metal in example 1.
As can be seen from fig. 2, the lithium-rich material with a disordered structure of the transition metal in a high valence state on the surface still has a spherical structure, and the surface is smoother than that before coating, indicating that more pores still exist.
Next, for the prepared lithium-rich material with disordered structure of transition metal in high valence state on the surface and the original lithium-rich cathode material Li1.2Mn0.54Ni0.13Co0.13O2The XPS test was performed, and the test result is shown in fig. 3, where 1 is a lithium-rich cathode material, and 2 is a lithium ion battery cathode material with a disordered structure of a high-valence transition metal.
From the peak of Mn2p in FIG. 3, it can be seen that 2p of the original lithium-rich material3/2Peak position 642.8eV, and 2p3/2And 2p1/2The binding energy difference value of (a) is 11.5eV, the 2p peak of Mn of the prepared lithium-rich material with the surface having the disordered structure of the high-valence transition metal shifts towards the direction of high binding energy compared with the peak of the original lithium-rich material, which shows that the valence of Mn on the surface in the material is increased, and the method is used for preparing the lithium-rich cathode material with the surface having the disordered structure of the high-valence transition metal;
the lithium-rich cathode material and the lithium-rich cathode material (Li) with disordered structures and high-valence transition metals on the surfaces, prepared in example 11.2Mn0.54Ni0.13Co0.13O2) The lithium ion battery is formed with a lithium plate, a polyolefin porous diaphragm and a commercial electrolyte to carry out electrochemical performance test; the test result is shown in fig. 4, where 1 is a lithium-rich cathode material, and 2 is a lithium ion battery cathode material with a disordered structure of a high-valence transition metal.
As can be seen from fig. 4, the lithium-rich cathode material having a disordered structure of transition metal in a high valence state on the surface has a specific discharge capacity of 260.37mAh/g at a current density of 30mA/g, a specific discharge capacity of 158.38mAh/g at a current density of 500mA/g, and the lithium-rich cathode material (Li) is obtained1.2Mn0.54Ni0.13Co0.13O2) The first discharge specific capacity is 229.36mAh/g under the current density of 30mA/g, and the discharge specific capacity is 124.78mAh/g under the current density of 500 mA/g.
Lithium-rich cathode material with disordered structure of transition metal with high valence state on surface and original lithium-rich material (Li)1.2Mn0.54Ni0.13Co0.13O2) The test result of the cycle performance curve of the formed lithium ion battery under 300mA/g is shown in figure 5, wherein 1 is a lithium-rich anode material, and 2 is a disordered structure lithium ion battery anode material with high-valence transition metal on the surface.
As can be seen from fig. 5, the lithium-rich cathode material with a disordered structure of the transition metal in a high valence state on the surface of the invention also has excellent cycle performance, and the capacity retention rate can reach 94% after 100 cycles.
In conclusion, the invention solves the problems that the existing lithium ion battery anode material is not easy to Li due to low conductivity and two-dimensional structure+The problems of low specific discharge capacity, poor rate capability and the like of the material caused by the problems of high pH value of the surface and the like of transmission and the like are solved, and the anode material of the lithium ion battery with the disordered structure and the high-valence transition metal on the surface of the anode material is treated by strong oxidizing acid and provided with the preparation method thereof.
The embodiments in the present description are described in a progressive manner, each embodiment focuses on differences from other embodiments, and the same and similar parts among the embodiments are referred to each other. The device disclosed by the embodiment corresponds to the method disclosed by the embodiment, so that the description is simple, and the relevant points can be referred to the method part for description.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (5)
1. A kind of strong oxidizing acid treats the positive pole material of the lithium ion battery with disordered structure of the transition metal of high valence state on the surface of the structure, characterized by that, including: the lithium ion battery comprises a lithium ion battery anode material and a disordered structure surface layer with high-valence transition metal;
the thickness of the disordered structure surface layer of the transition metal with the high valence state is 3-10nm, and the transition metal with the high valence state is Mn;
the anode material of the lithium ion battery is manganese-based anode material LiMnxM1-xO2 ,LiMnxM1-xPO4 ,LiMnxM1-xO4And yLi2MnO3·(1-y)LiMnxM1-xO2Wherein 0 is one or a mixture of several of<x≤1 ,0<Y is less than or equal to 1, M is one or more of Ni, Co, Fe, Ti, Zn, Nb, Cu, Mo, Ba, Ru, Ir, Sr, Cr, Y, Ga, K, Mg, V and Zr;
the preparation method of the disordered structure lithium ion battery anode material with the high-valence transition metal on the surface of the strong-oxidizing acid treatment structure comprises the following steps:
the method comprises the following steps: adding a proper amount of strong oxidizing acid into water, stirring until the mixture is uniformly mixed, and preparing a strong oxidizing acid solution;
step two: adding the lithium ion battery anode material into the solution obtained in the first step, stirring to fully oxidize transition metal ions on the surface of the lithium ion battery anode material, filtering, washing and drying;
step three: sintering the material dried in the second step to obtain the lithium ion battery anode material with high-valence transition metal on the surface;
the strong oxidizing acid in the step one is one of perchloric acid, perbromic acid, periodic acid, hypochlorous acid, persulfuric acid and dichromic acid; the sintering temperature in the third step is 400-.
2. The positive electrode material of the lithium ion battery with the disordered structure of the high-valence transition metal on the surface of the strong-oxidizing acid treatment structure as claimed in claim 1, wherein the concentration of the strong-oxidizing acid solution prepared in the first step is 0.1-2 g/L.
3. The positive electrode material of the lithium ion battery with the disordered structure of the transition metal with the high valence state on the surface of the strong oxidizing acid treatment structure as claimed in claim 1, wherein the mass ratio of the positive electrode material of the lithium ion battery and the strong oxidizing acid added in the second step is 1-100: 1.
4. The positive electrode material of the lithium ion battery with the disordered structure of the high-valence transition metal on the surface of the strong-oxidizing acid treatment structure as claimed in claim 1, wherein the specific process parameters in the second step are as follows: stirring for 0.5-2h, drying at 50-120 deg.C for 8-12 h.
5. The positive electrode material of the lithium ion battery with the disordered structure of the transition metal with the high-valence state on the surface of the strong-oxidizing acid treatment structure as claimed in claim 1, wherein the atmosphere in the sintering treatment in the third step is one or more of a nitrogen atmosphere, an argon atmosphere, a helium atmosphere and an oxygen atmosphere.
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| JP2000264638A (en) * | 1999-03-23 | 2000-09-26 | Toyota Central Res & Dev Lab Inc | Production of lithium manganese compound oxide for anode active substance of lithium secondary battery |
| CN104009220A (en) * | 2014-05-30 | 2014-08-27 | 厦门大学 | Method for treating manganese-based anode material |
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| JP2000264638A (en) * | 1999-03-23 | 2000-09-26 | Toyota Central Res & Dev Lab Inc | Production of lithium manganese compound oxide for anode active substance of lithium secondary battery |
| CN104009220A (en) * | 2014-05-30 | 2014-08-27 | 厦门大学 | Method for treating manganese-based anode material |
| CN105047905A (en) * | 2015-07-13 | 2015-11-11 | 中南大学 | Surface modification method of nickel-rich cathode material |
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