CN115050959A - Method for regulating and controlling surface interface of lithium-rich manganese-based positive electrode material by oxalic acid - Google Patents
Method for regulating and controlling surface interface of lithium-rich manganese-based positive electrode material by oxalic acid Download PDFInfo
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- oxalic acid
- lithium
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- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 title claims abstract description 162
- 235000006408 oxalic acid Nutrition 0.000 title claims abstract description 53
- 239000011572 manganese Substances 0.000 title claims abstract description 42
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 22
- 238000000034 method Methods 0.000 title claims abstract description 22
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 17
- 230000001105 regulatory effect Effects 0.000 title claims abstract description 16
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 15
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 15
- 230000001276 controlling effect Effects 0.000 title claims abstract description 8
- 239000000463 material Substances 0.000 claims abstract description 142
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- 238000001354 calcination Methods 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000008367 deionised water Substances 0.000 claims abstract description 8
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 8
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- 238000005303 weighing Methods 0.000 claims abstract description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical group [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- 238000003837 high-temperature calcination Methods 0.000 claims description 6
- 102000020897 Formins Human genes 0.000 claims description 5
- 108091022623 Formins Proteins 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 28
- 238000010306 acid treatment Methods 0.000 description 25
- 229910052596 spinel Inorganic materials 0.000 description 24
- 239000011029 spinel Substances 0.000 description 24
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- 239000013078 crystal Substances 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 5
- 238000013507 mapping Methods 0.000 description 5
- 239000002243 precursor Substances 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 230000002829 reductive effect Effects 0.000 description 4
- 239000007858 starting material Substances 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
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- 230000014759 maintenance of location Effects 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 150000007522 mineralic acids Chemical class 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 230000000087 stabilizing effect Effects 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000003321 amplification Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
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- 238000010438 heat treatment Methods 0.000 description 2
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- ZAUUZASCMSWKGX-UHFFFAOYSA-N manganese nickel Chemical compound [Mn].[Ni] ZAUUZASCMSWKGX-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
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- 238000003199 nucleic acid amplification method Methods 0.000 description 2
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- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000011282 treatment Methods 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 229910015118 LiMO Inorganic materials 0.000 description 1
- 229910015643 LiMn 2 O 4 Inorganic materials 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 229910021314 NaFeO 2 Inorganic materials 0.000 description 1
- 241000080590 Niso Species 0.000 description 1
- 238000001237 Raman spectrum Methods 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
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- 230000002572 peristaltic effect Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- XOFYZVNMUHMLCC-ZPOLXVRWSA-N prednisone Chemical compound O=C1C=C[C@]2(C)[C@H]3C(=O)C[C@](C)([C@@](CC4)(O)C(=O)CO)[C@@H]4[C@@H]3CCC2=C1 XOFYZVNMUHMLCC-ZPOLXVRWSA-N 0.000 description 1
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 235000002639 sodium chloride Nutrition 0.000 description 1
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- 150000003624 transition metals Chemical group 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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- Y02E60/10—Energy storage using batteries
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- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention provides a method for regulating and controlling a surface interface of a lithium-rich manganese-based positive electrode material by oxalic acid, which comprises the following steps of: step 1, preparing the concentration of 0.05mol L ‑1 ‑0.2molL ‑1 Oxalic acid solution of (1); step 2, preparing the prepared Li 1.2 Ni 0.24 Mn 0.56 O 2 Weighing 0.8g of materials, placing the materials in a 50mL beaker, adding 10mL of oxalic acid solution, and placing the materials in a water bath kettle with the set temperature of 25 ℃ for rapid reaction for 10 min; and 3, washing the material after the reaction in the step 2 by using deionized water and ethanol, filtering, drying in a vacuum oven at the temperature of 80 ℃ for 12 hours, and then carrying out secondary calcination to obtain a modified sample. The invention aims to provide a method for improving lithium-rich manganese-based positive electrode material and improving the electrochemical performance of the lithium-rich manganese-based positive electrode material.
Description
Technical Field
The invention belongs to the field of batteries, and particularly relates to a method for regulating and controlling a surface interface of a lithium-rich manganese-based positive electrode material by oxalic acid.
Background
In recent years, researchers have proposed strategies for manipulating the surface interface of materials using inorganic acids, where the primary mechanism is H of the acid solution + Li capable of being attached to surface of material + Generation of Li + /H + The displacement reaction thus reconstructs the surface of the material. Wang et al, which uses a hydrochloric acid solution to treat the surface of a material, have shown that sufficient lithium vacancies are generated on the surface of the material due to proton exchange reaction, so that the surface structure of the material is converted into a spinel phase. The treated material shows excellent electrochemical performance, and has 313.6mAhg at 0.1C -1 Initial capacity at 1C of 204.0mAhg -1 And 197.5mAhg after 100 cycles -1 The specific capacity of (a). Maibach et al treated the surface of the material with phosphoric acid due to Li on the surface of the material + And H + A displacement reaction occurs to cause lattice distortion, and the metastable O on the surface of the material is subjected to heat treatment and structural reconstruction accompanied by surface layer opposite rock salt/spinel conversion n- Is easily converted into O 2 Is released from the surface of the material in advance. The results show that the surface lattice plays a crucial role in the electrochemical performance of the lithium-rich cathode material. McCloskey et al used sulfuric acid to study the effect of acid treatment on materials and they quantified the effect on Li + The extent to which lattice oxygen participates in charge compensation during removal. They propose that the initial capacity of the raw material is not reduced by the acid treatment, but rather the long cycle capacity and rate capability of the material are improved. Although the inorganic acid can react with the lithium rich material to produce Li + /H + However, the inorganic acid will indiscriminately dissolve the Ni \ Mn elements on the surface of the material, and the Ni content in the surface of the obtained material is still relatively high, and the material cannot play a role in stabilizing the structure.
The oxalic acid treatment, on the one hand, results in H in the acid solution compared to the mineral acid + Li with surface of material + Generation of Li + /H + Performing replacement reaction; on the other hand, the complexation of oxalate will further restructure the surface of the material, and the material will beThe surface Ni element is extracted and retained with the surface Mn element, thereby constructing and obtaining a Mn-rich surface which is more stable.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides a method for regulating and controlling the surface interface of a lithium-rich manganese-based positive electrode material by oxalic acid.
The surface structure of the material is controlled by regulating the concentration of the oxalic acid solution, and the mechanism of the invention is deeply researched by performing characterization analysis on various physical properties of the material and testing and analyzing the electrochemical performance of the material. The result shows that the initial capacity, the cycle retention rate and the rate performance of the material are fully improved under the modification.
The invention adopts the following technical scheme:
a method for regulating and controlling a surface interface of a lithium-rich manganese-based positive electrode material by oxalic acid comprises the following steps:
and 3, washing the material after the reaction in the step 2 by using deionized water and ethanol, filtering, drying in a vacuum oven at the temperature of 80 ℃ for 12 hours, and then carrying out secondary calcination to obtain a modified sample.
The concentration of oxalic acid in the step 1 is 0.05mol L -1 。
The concentration of oxalic acid in the step 1 is 0.1molL -1 。
The concentration of oxalic acid in the step 1 is 0.2molL -1 。
The calcining atmosphere is argon, and the calcining temperature is 5 ℃ for min -1 The temperature rise rate of (2) is increased to 900 ℃ and high-temperature calcination is carried out for 2 h.
The invention has the beneficial effects that: the Mn-rich spinel structure surface is obtained, and the stability and rate capability of the material are improved.
Drawings
FIG. 1(a) is a SEM and elemental distribution diagram of LLO;
FIG. 1(b) is an SEM and elemental distribution plot of OX-0.05;
FIG. 1(c) is an SEM and elemental distribution plot of OX-0.1;
FIG. 1(d) is an SEM and elemental profile of OX-0.2;
FIG. 2(a) is an XRD spectrum of LLO;
FIG. 2(b) is an XRD pattern of OX-0.05;
FIG. 2(c) is an XRD pattern of OX-0.1;
FIG. 2(d) is an XRD pattern of OX-0.2;
FIG. 3(a) is an XRD refinement pattern of LLO;
FIG. 3(b) is an XRD refinement pattern of OX-0.05;
FIG. 3(c) is an XRD refinement profile of OX-0.1;
FIG. 3(d) is an XRD refinement pattern of OX-0.2;
FIG. 4(a) is a Raman refined spectrum of LLO;
FIG. 4(b) is a Raman refinement profile of OX-0.05;
FIG. 4(c) is a Raman refinement spectrum of OX-0.2;
FIG. 4(d) is a Raman refinement spectrum of OX-0.2;
FIG. 5(a) is a TEM, HR-TEM, FFT and interlayer spacing plot of LLO samples;
FIG. 5(b) is a TEM, HR-TEM, FFT and interlayer spacing plot of OX-0.1 samples;
FIG. 5(c), FIG. 5(d), FIG. 5(e), FIG. 5(f), FIG. 5(g) are the elemental distribution plots for the OX-0.1 samples, respectively;
FIG. 6(a) is the first turn charge-discharge curve for all samples;
FIG. 6(b) is the rate capability of all samples;
FIG. 6(C) is the cycle performance at 1C for all samples;
FIG. 6(d) is the cycle performance at 5C for all samples;
FIG. 7(a) is a 1st,5st,10th,50th,100th,200th charge-discharge curves of LLO in a voltage range of 2.0-4.8V and with a magnification of 1C;
FIG. 7(b) is a 1st,5st,10th,50th,100th,200th charge-discharge curves of OX-0.05 in a voltage range of 2.0-4.8V at a magnification of 1C;
FIG. 7(C) is a 1st,5st,10th,50th,100th,200th charge-discharge curves of OX-0.1 in a voltage range of 2.0-4.8V at a magnification of 1C;
FIG. 7(d) is a 1st,5st,10th,50th,100th,200th charge-discharge curves of OX-0.2 at a voltage interval of 2.0-4.8V and a magnification of 1C;
FIG. 8(a) is a dQ/dV curve of LLO in voltage interval of 2.0-4.8V at 5th,10th,40th,70th,100th at a magnification of 1C;
FIG. 8(b) is a dQ/dV curve of OX-0.05 at 5th,10th,40th,70th,100th at a magnification of 1C in a voltage interval of 2.0-4.8V;
FIG. 8(C) is a dQ/dV curve of OX-0.1 at 5th,10th,40th,70th,100th at a magnification of 1C in a voltage interval of 2.0-4.8V;
FIG. 8(d) is a dQ/dV curve of OX-0.2 at 5th,10th,40th,70th,100th at a magnification of 1C in a voltage interval of 2.0-4.8V;
FIG. 9(a) is a TEM and FFT image of LLO sample after cycling 200 cycles at 1C magnification;
FIG. 9(b) is a TEM and FFT image of OX-0.1 sample after cycling 200 cycles at 1C magnification;
fig. 10(a) is a raman spectrum of all samples after cycling 200 cycles at 1C magnification;
FIG. 10(b) is the impedance and XPS after 200 cycles at 1C magnification for all samples;
FIG. 10(C) is Mn2P after 200 cycles at 1C magnification for all samples;
FIG. 10(d) is F1s after 200 cycles at 1C magnification for all samples;
fig. 11 is a schematic flow chart of oxalic acid treatment of the lithium-rich manganese-based positive electrode material.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention are described below clearly and completely, and it is obvious that the described embodiments are some, not all embodiments of the present invention. All other embodiments, which can be obtained by a person skilled in the art without inventive step based on the embodiments of the present invention, are within the scope of protection of the present invention.
As shown in fig. 11, the method for regulating and controlling the surface interface of the lithium-rich manganese-based positive electrode material by oxalic acid comprises the following steps:
and 3, washing the material after the reaction in the step 2 by using deionized water and ethanol, filtering, drying in a vacuum oven at the temperature of 80 ℃ for 12 hours, and then carrying out secondary calcination to obtain a modified sample.
The concentration of oxalic acid in the step 1 is 0.05mol L -1 。
The concentration of oxalic acid in the step 1 is 0.1molL -1 。
The concentration of oxalic acid in the step 1 is 0.2molL -1 。
The calcining atmosphere is argon, and the calcining temperature is 5 ℃ for min -1 The temperature rise rate of (2) is increased to 900 ℃ and high-temperature calcination is carried out for 2 h.
Examples
For the starting material Li 12 Ni 0.24 Mn 0.56 O 2 The detailed preparation process is as follows:
specifically, a continuous stirring reaction kettle is adopted to carry out a coprecipitation experiment of carbonate so as to obtain a carbonate precursor.
The specific process is as follows: first, a transition metal sulfate (MnSO) 4 ·H 2 O and NiSO 4 ·6H 2 O) is prepared according to the molar ratio of 1.4:0.6 and the concentration is 2mol L -1 A salt solution. Then, the concentrations were set to 2mol L -1 Sodium carbonate solution (Na) 2 CO 3 ) As a precipitant in the reaction process and with a concentration of 0.2mol L -1 Ammonia water solution (NH) 4 ·H 2 O) asIs a complexing agent. A certain amount of base solution (deionized water) was added to the reaction kettle before the start of the experiment, the pH meter was calibrated, and then the reaction kettle was fixed in a water bath set to a temperature of 50 ℃. Thereafter, the three solutions were continuously added to a 500mL glass reaction vessel by a peristaltic pump at a flow rate. The pH value of the reaction kettle is regulated and controlled to be 8 +/-0.05 by adjusting the feeding speed of the sodium carbonate solution, and the stirring speed of the reaction kettle is controlled to be 1000 rpm. After continuous reaction for 10h, closing the feeding, aging the reaction kettle for 30min, collecting the precipitate in the reaction kettle, and removing SO by suction filtration and washing with deionized water 4 2- And then, putting the precipitate into a vacuum oven for drying for 12 hours, wherein the temperature of the oven is 120 ℃, and respectively obtaining precursors with different nickel contents after drying.
Mixing the obtained precursor with Li source 2 CO 3 Fully grinding the materials in a quartz mortar according to a designed proportion, and finally calcining the materials at a high temperature to obtain a finished product Li 1.2 Ni 0.24 Mn 0.56 O 2 . The procedure for the high temperature calcination is as follows: the heating rate is 5 ℃ for min -1 Pre-calcining at 500 deg.c from normal temperature for 5 hr, calcining at 850 deg.c from 500 deg.c for 12 hr, and cooling naturally to room temperature.
The specific experimental method for regulating the surface of the material by the oxalic acid solution is as follows:
first, the concentrations were set to 0.05mol L each -1 ，0.1molL -1 ,0.2molL -1 The oxalic acid solution of (2) is ready for use. Secondly, the prepared Li 1.2 Ni 0.24 Mn 0.56 O 2 0.8g of the material is weighed and placed in a 50mL beaker, 10mL of oxalic acid solution is added and the beaker is placed in a water bath kettle with the set temperature of 25 ℃ for 10min for rapid reaction. And then washing the reacted material by using deionized water and ethanol, filtering, drying in a vacuum oven at the temperature of 80 ℃ for 12h, and then carrying out secondary calcination. The calcining atmosphere is argon, and the calcining procedure is to use 5 ℃ for min -1 The temperature is raised to 900 ℃ at the temperature raising rate, and the modified sample is obtained after the high-temperature calcination is carried out for 2 hours. According to the different concentrations of the added oxalic acid solution, the obtained samples are respectively marked as OX-0.05, OX-0.1, OX-0.2. Wherein the starting material also requires the above operation in the treatment system of deionized water for removing H from water + The effect on the experiment was noted LLO.
Results and discussion
Physical characterization of oxalic acid-treated materials
Fig. 1(a) -fig. 1(d), as shown in the figure, all samples are regular spherical particle structures, and the morphology of the precursor is well inherited. The particle diameter of the acid treated material was reduced to a different extent compared to LLO due to the acid treatment. Secondly, since the carbonate precursor is CO during the conversion from carbonate to oxide during the high temperature calcination process 2 And when the gas is released, the reason can be seen from a high-power figure of the material, the LLO material is formed by loose and piled submicron primary particles, and the surface of the material is loose and porous. This structure often results in the electrolyte being prone to encroaching into the bulk of the material and side reactions that can affect the electrochemical performance of the cell. In the sample treated by oxalic acid, the surface of the material is gradually compacted along with the increase of the concentration of the acid, so that a compact surface structure is formed, and the main body of the material is prevented from being directly corroded by electrolyte. In order to explore the influence of acid treatment on the distribution of elements on the surface of a material, mapping tests are carried out on three elements of Ni, Mn and O of four materials, as shown in the figure, the leftmost element is the Ni element, the middle element is the Mn element, and the rightmost element is the O element.
To further verify whether the Ni element was reduced, the sample was subjected to ICP-OES characterization test, and the results are shown in table 1, by testing Mn of LLO: the Ni value was 2.2099, OX-0.05 was 2.2454, OX-0.1 was 2.2801, and OX-0.2 was 0.2608, and it was found by comparison that the manganese-nickel ratio in the material was higher than that as the acid treatment proceeded, indicating that not only Li occurred during the organic acid treatment + /H + Displacement reactionThe complexation of oxalate on metal ions also occurs, Ni on the surface of the material is extracted, the surface structure of the material is further regulated, and the decrease of the OX-0.2 manganese-nickel ratio indicates that the higher the acid content is, the better the acid content is, and the excessive dissolution on the surface can be caused by too high the acid content, so that the structural stability is not good.
TABLE 1 ICP results for all materials
As shown in FIGS. 2(a) -2 (d), wherein all the diffraction peaks of the material are substantially identical, indicating hexagonal alpha-NaFeO 2 Structure belonging to the R-3m space group, typical of layered structure, corresponding to LiMO of the material 2 Structure of phase (M is transition metal). In addition, some weak peaks appear in the interval of 20 ° to 25 °, which is attributed to Li 2 MnO 3 LiM of phase (C2/m space group) 6 The superlattice structure of (1). Where all samples were observed to have large peak intensities and narrow half-peak widths, demonstrating good crystallinity for all materials. Secondly, the two sets of characteristic peaks (006)/(012) and (018)/(110) for each sample have distinct splitting phenomena, which demonstrates that the material has a good lamellar ordered structure. When the peaks (003), (104) and (107) of the material are respectively observed in an enlarged manner, the peaks (003) and (104) of the acid-treated material are slightly shifted to a low angle, and the shifting amplitude is gradually increased along with the increase of the oxalic acid concentration, which indicates that the interlayer spacing of the material is increased, and the migration of Li ions in the charge and discharge process of the material is facilitated. While the amplified (107) peak can be observed as a merged peak with one (017) peak at 58.3 degrees, which is indexed by standard cards and is spinel LiMn 2 O 4 The (511) peak of the phase shows that the material generates a spinel heterogeneous layer after surface conditioning.
In order to obtain more detailed and accurate information such as lattice parameters, XRD of all materials was further refined according to a two-phase model of hexagonal phase R-3m and monoclinic phase C2/m, and the results are shown in FIGS. 3(a) -3 (d), and specific statistics are shown in the table2, in (c). It can be seen from figures 3(a) -3 (d) that the refined calculated curves for the four samples substantially matched the actual test curves,
are all less than 10%, variance X 2 And the minimum value indicates that the fine correction result is accurate and reliable. Analyzing the data in the table can lead to the following conclusions: the value a and the value c of the sample after acid treatment are both increased to a certain extent along with the increase of the acid concentration; the c/a values are all larger than 4.9, which shows that the material has a good layered structure; third, the I (003)/(104) of all samples meets the requirement of the lowest cation mixed-arrangement degree (> 1.2), and the I (003)/(104) ratio of the material is increased along with the increase of the acid concentration, which indicates that the acid treatment can further inhibit the cation mixed-arrangement of the material, because the cation mixed-arrangement is generally formed by Ni 2+ Substituting Li in the lithium layer + Due to this, it can be deduced that the oxalic acid treatment extracted Ni of the material 2+ 。
TABLE 2 lattice parameters after refinement of all materials
The structure of the material was analyzed using raman, as shown in fig. 3 (a). Electrode material at 480cm -1 And 596cm -1 Due to O-M-O bending (E) in hexagonal phase R-3M g ) And M-O stretching (A) 1g ) And at 365cm -1 And 420cm -1 Weak Raman peak and Li at the purple dotted line box 2 MnO 3 In this connection, it is noted that when the concentration of the acid treatment is increased to 0.1mol L -1 At 625cm -1 A weak shoulder seam appears due to the formation of spinel phase at the surface of the material. The absence of significant shoulder seams in the OX-0.05 samples was attributed to the fact that the acid concentration was not high and the spinel phase formed was too little to be detected.
To investigate the chemical valence states of the individual elements in a sample and thus better investigate the mechanism of the material under acid treatment, XPS was used for each individual elementThe material was analyzed as shown in fig. 4(a) -4 (d). As shown in FIG. 4(b), it can be observed that the diffraction peaks representing carbonate near 290eV are very weak compared with LLO as the acid treatment proceeds, which indicates that residual lithium on the surface of the material is removed completely by the acid treatment, thereby avoiding the generation of unfavorable CO during the charging and discharging processes 2 A gas. As shown in FIG. 4(c), Ni in four samples is obtained by fitting peaks of the fine spectrum and counting different valence states of Ni element 2+ The ratio of (A) to (B) decreases with increasing acid treatment concentration, and in combination with the analysis characterized above, indicates that Ni is present during acid treatment 2+ Is complexed by oxalate and is released from the surface of the material. FIG. 4(d), wherein Mn has a valence of upsilon Mn Energy difference delta E between two peaks in the map 3s Proportional, the specific formula is as follows:
υ Mn ＝9.67-1.27ΔE 3s (4-1)
by calculation, the valence states of the materials in the formula collected Mn are +3.94, +3.97, +4.07, +4.26 respectively. This is due to Li + and Ni on the surface of the material 2 + the reason for charge compensation after being extracted from the material.
TEM analysis gave more detailed surface microstructures as shown in fig. 5(a) -5 (g). TEM and elemental distribution (EDS mapping) characterization analyses were performed on LLO and OX-0.1 materials. The lattice fringes on the TEM images of both materials are clearly visible, indicating that the samples are well crystalline. Wherein both the bulk portion and the surface region portion of the LLO material exhibit identical lattice fringes, indicating that no other heterogeneous phase is present in the LLO material. The region I is selected from the LLO material for amplification analysis, and the lattice spacing of the material is 0.4708nm, and the (001) crystal face is analyzed as C2/m by combining FFT. Unlike LLO materials, a thin heterogeneous layer exists on the OX-0.1 surface. The region I of the bulk portion of the OX-0.1 material was analyzed under magnification, giving a (021) plane with a lattice spacing of 0.3232nm and a C2/m in the bulk portion of the material. Meanwhile, the surface heterogeneous layer region II of the OX-0.1 material is subjected to amplification analysis, and the surface heterogeneous layer region II is expressed by (111) crystal faces of spinel phase with the lattice spacing of 0.4743 nm. A large number of researches prove that the spinel layer generated on the surface of the material which is not subjected to electrochemical tests plays an important role in stabilizing the structure of the material and improving the electrochemical performance. EDS mapping was performed on the surface elements of the OX-0.1 samples to analyze the distribution of the surface elements, as shown in FIGS. 5(c) -5 (g), with Ni element at the leftmost side, Mn element in the middle, and O element at the rightmost side. From the EDS Mapping chart, it is clearly observed that the Mn and O elements in the OX-0.1 sample are uniformly distributed, while the Ni element is non-uniformly distributed on the surface of the material, which is consistent with the Mapping result in the SEM picture above, and shows that the active metal nickel in the material is extracted when the lithium-rich material is treated by oxalic acid.
Electrochemical performance and structural stability analysis after circulation of oxalic acid treatment material
To study the electrochemical performance of the oxalic acid treated materials, all materials were prepared into button half cells for electrochemical testing and analysis. For example, as shown in fig. 6(a), the first-cycle charge-discharge curves of the samples each showed the typical redox characteristics of the lithium-rich material, but the oxalic acid-treated sample showed better first-cycle Coulombic Efficiency (CE), wherein 0.1mol L -1 The first-pass coulombic efficiency of the oxalic acid treated sample at the concentration was 82.0%, which was 12% higher than the original material. At the same time, it was found that the charging curves of the four materials were nearly identical, indicating that the oxalic acid treated material possessed more reversible oxygen redox reactions in the first round. FIG. 6(b) is a clear observation that the oxalic acid treated material has better performance at high rate, especially at 5C rate, the specific capacity of the sample at OX-0.1 is 169.6mAhg -1 Much higher than 137.2mAhg- 1 。
To further verify the cycle performance of the treated material, long cycle tests were performed on the treated sample and the original material at 1C and 5C magnifications, respectively, as shown in fig. 6(C) and 6 (d). As shown, LLO provided an initial specific discharge capacity of only 183.3mAhg -1 And only 147.1mAhg remained after 200 cycles -1 The specific capacity and the storage rate of the lithium ion battery are only 80.3 percent. And initial specific discharge capacities for OX-0.05, OX-0.1, and OX-0.2 samples were 196.5, 199.3, and 203.0mAhg, respectively -1 . After 300 cycles, 164.7, 179.5 and 148.0mAhg remained -1 The specific capacity and the capacity retention rate of (2) are respectively 83.8%, 90.1% and 72.9%. It was found that the acid treated material was able to increase the specific capacity of the material, and although the initial specific capacity of the OX-0.2 sample was the highest, the cycling stability was destroyed because the acid solution with too high concentration excessively eroded the surface of the material, thereby destroying the structure of the material, so that it could not be kept stable during cycling. As shown in FIG. 6(d), OX-0.1 was 25.32mAhg higher than the starting material at the initial stage of the cycle -1 And after 300 cycles, the material still has 26.72mAhg higher than the original material -1 。
In addition to the above electrochemical performance, further focusing on the voltage decay of each material during the cycle, fig. 7(a) -7 (d) respectively plot the charge and discharge curves of each material at 1st,5st,10th,50th,100th,200th in the voltage interval of 2.0-4.8V at a rate of 1C, and label the voltage value of the decay, and the voltage of 200 th. Wherein, the OX-0.1 sample has 3.0V of median voltage after 200 circles, the voltage loss is 0.70V compared with the original cycle median voltage of 2.79V and the voltage loss is 0.85V; after OX-0.05 sample circulation, the median voltage is 2.91V, and the voltage loss is 0.75V; the OX-0.2 sample has a median voltage of 2.74V after circulation, and a voltage loss of 0.91V, which is superior to that of other materials in all aspects. But the lifting amplitude is relatively insignificant, and a large lifting space is still left.
It can be found that the voltage decay is most obvious when the material is in the first 100 circles, and for further study on this phenomenon, the dQ/dV maps of 5th,10th,40th,70th and 100th in the first one hundred circles of each material are plotted, as shown in fig. 8(a) to 8 (d). The reduction peak is mainly concerned in the dQ/dV spectrum, wherein the reduction peak in the 2.5-3.5V interval corresponds to Mn 3+ /Mn 4+ The reduction process of (2): the reduction peak in the interval of 3.5-4.5V corresponds to Ni 2+ /Ni 4+ The reduction process of (1). For all samples, a tendency towards a low angular shift of the reduction peak was found, wherein a low angular shift of the reduction peak of Mn represents a gradual material transition fromTransformation of the lamellar phase into the spinel phase. Mn of LLO, OX-0.05, OX-0.1 and OX-0.2 as shown in FIGS. 8(a) to 8(d) 4+ /Mn 3+ The potential offset difference amounts are 209mV, 195mV, 155mV and 349mV respectively. The acid concentration is 0.05mol L -1 And 0.1mol L -1 The amount of shift is less than LLO, and when the acid concentration is 0.2mol L -1 The amount of time shift was the greatest, indicating that the higher the acid treatment concentration was not, the better, and the result was also consistent with the tendency of voltage decay. In addition, the remaining samples, with the exception of the LLO sample, all had a small peak in the 3.0-3.5V region, indicating that the acid treated sample had a spinel phase prior to recycle, consistent with the characterization of XRD, Raman and TEM. Meanwhile, the spinel phase plays a role in inhibiting voltage attenuation under the condition of a proper amount.
In order to verify whether the structure of the material after circulation is stable, the button half cells of all samples which are circulated for 200 circles at a magnification of 1C are disassembled in a glove box, the electrode plates after circulation are taken out, and TEM, Raman, EIS and XPS tests are carried out on the electrode plates to explore the structure of the material after circulation. As shown in FIGS. 9(a) to 9(b), a heterogeneous layer with the thickness of about 3nm still exists on the surface of the OX-0.1 sample, and after Fourier transform, the index is the (111) crystal face of the spinel phase after being compared with the standard card. The analysis of the interior of the material can observe that the internal structure is consistent with that before circulation, the crystal lattice stripes are clear, and the material is an obvious layered structure. On the other hand, as compared with the OX-0.1 sample, a heterogeneous layer with a thickness of 9nm appeared on the surface, and the heterogeneous layer was found to be a characteristic of a distinct cubic phase after Fourier transform, and was also judged to be a (111) plane of a spinel phase. The analysis of the interior of the material can observe that the internal structure is consistent with that before circulation, the crystal lattice stripes are clear, and the material is an obvious layered structure. Compared with an OX-0.1 sample, the original sample has the advantages that a heterogeneous layer with the thickness of 9nm appears on the surface of the original sample, the characteristic that the heterogeneous layer is an obvious cubic phase can be found after Fourier transform, the heterogeneous layer is judged to be a spinel phase, a small part of area in the material still keeps a lamellar structure, and the rest area shows a mixed structure of the spinel phase and the lamellar phase, so that the structure of the material generates a serious lamellar phase in the circulation process of the original sampleTransformation to spinel phase. FIG. 10(a), E can be found as it is g And A 1g The peak at (a) is not evident, indicating that the layered structure has been destroyed, consistent with TEM conclusions. FIG. 10(b) is an impedance analysis after the circulation of materials, each curve of which is composed of two semicircles, in which the high frequency region and the surface film impedance (R) are sf ) In relation to the transfer resistance (R) of the material in the intermediate frequency region ct ) It is related. For Rsf, LLO 88.83 Ω, OX-0.05 88.72 Ω, OX-0.1 50.18 Ω, OX-0.2 109.1 Ω, R for OX-0.1 samples sf At a minimum, the SEI film indicating its surface is also the thinnest, while OX-0.2 is instead larger than the starting material indicating that the concentration is not as high as possible with acid treatment. While a certain suppression is obtained for Rs, although the relative small value of OX-0.1, overall Rs per material is large and needs further improvement. FIGS. 10(c) -10 (d), the Mn of the material after recycling due to the treatment with oxalic acid carried out can be found 3+ The amount of (A) is obviously inhibited, which also represents that the lamellar phase of the surface of the material is inhibited to be converted into the spinel phase, and the analysis of the F1s orbit can find that the peak represents the proportion of the M-F binding energy, OX-0.1 is the minimum, which indicates that the spinel phase generated after oxalic acid treatment also protects the material from the corrosion of electrolyte, while the proportion of OX-0.2 is higher than the original, which further proves that the higher the acid concentration is, the better the material is.
Ni-60 sample Li selected by the invention 1.2 Ni 0.24 Mn 0.56 O 2 As a modified sample, a heterogeneous layer of spinel was formed on the surface of the material by a simple oxalic acid treatment. The thin spinel layer has outstanding effects on stabilizing the structural stability of the material and improving the electrochemical performance. The crystal structure, the change of electrochemical properties, the structural stability and the like of the sample before and after oxalic acid treatment are comprehensively analyzed through physical characterization and electrochemical test, and the optimal treatment condition is selected.
(1) Through SEM test, the diameter of the secondary particles of the material after acid treatment is reduced, and the surface is gradually changed from a loose porous structure to a compact structure; XRD and XPS demonstrated that the material was treated with acidThe spinel phase is generated in the process, and the sample after acid treatment, particularly 0.1molL can be obtained by carrying out TEM, Raman, impedance and XPS tests on the circulated sample and carrying out comprehensive analysis -1 The oxalic acid treated samples had the best structural stability, indicating that constructing a spinel layer prior to cycling was beneficial in inhibiting structural transformation during cycling.
(2) After electrochemical testing of the acid treated samples, the comparison results showed 0.1mol L -1 Oxalic acid is the optimal treatment condition, the coulombic efficiency of the first circle of the material is the highest, the capacity retention rate of 200 circles of 1C circulation is 90.1% which is higher than 80.3% of the original shape, the excellent circulation stability is shown, and the method has great significance for prolonging the service life of the battery. Secondly, the specific discharge capacity of the OX-0.1 sample at a high rate of 5C was 169.6mAhg -1 Much higher than 137.2mAhg of the original material -1 This is due to the unique three-dimensional structure of the surface spinel layer favoring Li + And (4) diffusion.
Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (5)
1. A method for regulating and controlling a surface interface of a lithium-rich manganese-based positive electrode material by oxalic acid is characterized by comprising the following steps:
step 1, preparing the concentration of 0.05mol L -1 -0.2molL -1 Oxalic acid solution of (1);
step 2, preparing the prepared Li 1.2 Ni 0.24 Mn 0.56 O 2 Weighing 0.8g of materials, placing the materials in a 50mL beaker, adding 10mL of oxalic acid solution, and placing the materials in a water bath kettle with the set temperature of 25 ℃ for rapid reaction for 10 min;
and 3, washing the material after the reaction in the step 2 by using deionized water and ethanol, filtering, drying in a vacuum oven at the temperature of 80 ℃ for 12 hours, and then carrying out secondary calcination to obtain a modified sample.
2. The method for regulating the surface interface of the lithium-rich manganese-based positive electrode material by using the oxalic acid as claimed in claim 1, wherein the concentration of the oxalic acid in the step 1 is 0.05mol L -1 。
3. The method for regulating the surface interface of the lithium-rich manganese-based positive electrode material by using the oxalic acid as claimed in claim 1, wherein the concentration of the oxalic acid in the step 1 is 0.1mol L -1 。
4. The method for regulating the surface interface of the lithium-rich manganese-based positive electrode material by using the oxalic acid as claimed in claim 1, wherein the concentration of the oxalic acid in the step 1 is 0.2mol L -1 。
5. The method for regulating and controlling the surface interface of the lithium-rich manganese-based positive electrode material by using the oxalic acid as claimed in claim 1, wherein in the step 3, the calcining atmosphere is argon, and the calcining time is 5 ℃ for min -1 The temperature rise rate of (2) is increased to 900 ℃ and high-temperature calcination is carried out for 2 h.
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