CN115594235A - Preparation method and application of sodium-ion battery negative electrode material - Google Patents
Preparation method and application of sodium-ion battery negative electrode material Download PDFInfo
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- CN115594235A CN115594235A CN202211506542.7A CN202211506542A CN115594235A CN 115594235 A CN115594235 A CN 115594235A CN 202211506542 A CN202211506542 A CN 202211506542A CN 115594235 A CN115594235 A CN 115594235A
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- ion battery
- sodium
- calcium
- aluminum
- negative electrode
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- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 49
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 239000007773 negative electrode material Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000000460 chlorine Substances 0.000 claims abstract description 31
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 29
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000002699 waste material Substances 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 16
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 12
- 238000003756 stirring Methods 0.000 claims description 31
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 28
- 229910052782 aluminium Inorganic materials 0.000 claims description 27
- 239000000463 material Substances 0.000 claims description 27
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 25
- 239000011575 calcium Substances 0.000 claims description 25
- 229910052791 calcium Inorganic materials 0.000 claims description 23
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 21
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 17
- 239000007787 solid Substances 0.000 claims description 17
- 238000001914 filtration Methods 0.000 claims description 15
- 150000002221 fluorine Chemical class 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 13
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 12
- 229910052708 sodium Inorganic materials 0.000 claims description 12
- 239000011734 sodium Substances 0.000 claims description 12
- 239000000725 suspension Substances 0.000 claims description 12
- -1 calcium-aluminum-fluorine salt Chemical compound 0.000 claims description 10
- 239000010941 cobalt Substances 0.000 claims description 10
- 229910017052 cobalt Inorganic materials 0.000 claims description 10
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 8
- 229910052759 nickel Inorganic materials 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 6
- 239000010405 anode material Substances 0.000 claims description 6
- 239000000706 filtrate Substances 0.000 claims description 5
- 239000002244 precipitate Substances 0.000 claims description 5
- CSDQQAQKBAQLLE-UHFFFAOYSA-N 4-(4-chlorophenyl)-4,5,6,7-tetrahydrothieno[3,2-c]pyridine Chemical compound C1=CC(Cl)=CC=C1C1C(C=CS2)=C2CCN1 CSDQQAQKBAQLLE-UHFFFAOYSA-N 0.000 claims description 4
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 4
- 239000000920 calcium hydroxide Substances 0.000 claims description 4
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 4
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 4
- 239000000292 calcium oxide Substances 0.000 claims description 4
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims 1
- 229910052731 fluorine Inorganic materials 0.000 claims 1
- 239000011737 fluorine Substances 0.000 claims 1
- 239000010406 cathode material Substances 0.000 abstract description 10
- ULGYAEQHFNJYML-UHFFFAOYSA-N [AlH3].[Ca] Chemical compound [AlH3].[Ca] ULGYAEQHFNJYML-UHFFFAOYSA-N 0.000 abstract description 5
- 239000002351 wastewater Substances 0.000 abstract description 4
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 3
- 150000002739 metals Chemical class 0.000 abstract description 3
- 239000002131 composite material Substances 0.000 abstract description 2
- 230000008929 regeneration Effects 0.000 abstract 1
- 238000011069 regeneration method Methods 0.000 abstract 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 6
- 239000002033 PVDF binder Substances 0.000 description 6
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 6
- 239000011572 manganese Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 238000002386 leaching Methods 0.000 description 4
- 229910052748 manganese Inorganic materials 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 229910052761 rare earth metal Inorganic materials 0.000 description 4
- 150000002910 rare earth metals Chemical class 0.000 description 4
- 238000010183 spectrum analysis Methods 0.000 description 4
- 239000006245 Carbon black Super-P Substances 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 239000006258 conductive agent Substances 0.000 description 3
- 239000011889 copper foil Substances 0.000 description 3
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000006298 dechlorination reaction Methods 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 229910018626 Al(OH) Inorganic materials 0.000 description 1
- HFCVPDYCRZVZDF-UHFFFAOYSA-N [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O Chemical compound [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O HFCVPDYCRZVZDF-UHFFFAOYSA-N 0.000 description 1
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/006—Compounds containing, besides nickel, two or more other elements, with the exception of oxygen or hydrogen
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/78—Compounds containing aluminium and two or more other elements, with the exception of oxygen and hydrogen
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/54—Reclaiming serviceable parts of waste accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/85—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by XPS, EDX or EDAX data
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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Abstract
The invention relates to a preparation method and application of a sodium-ion battery negative electrode material. Compared with the prior art, the method not only realizes the regeneration and the use of waste residues generated by the chlorine-containing wastewater precipitated by a calcium-aluminum salt method, but also effectively recycles valuable metals of the waste lithium ion battery, and develops a novel sodium ion battery cathode material; the method is green and environment-friendly, and has low cost and simple process. The composite material prepared by the invention is used as a sodium ion battery cathode material and has good circulation stability.
Description
Technical Field
The invention relates to the technical field of preparation of a negative electrode material of a sodium-ion battery, in particular to a preparation method and application of the negative electrode material (containing a fluorine salt of nickel, cobalt, manganese, calcium and aluminum).
Background
With the development of portable electronic devices and all-electric or hybrid electric vehicles, lithium ion batteries have gained wide use. However, the drastic increase in the use of lithium ion batteries has led to a shortage of lithium resources. In contrast, sodium ion batteries have been receiving particular attention because of their abundant and widespread sodium reserves in the global area, and they are similar to lithium ions in terms of structure, components, and ion migration and storage mechanisms, which allows the research techniques of both systems to be shared. However, sodium ions have a larger ionic radius than lithium ions, and thus are not suitable for sodium ion batteries, which are widely used as negative electrode materials for lithium ion batteries. Therefore, the development of the negative electrode material of the sodium ion battery is very important for the popularization and application of the sodium ion battery.
The negative electrode material of the sodium ion battery is roughly classified into 5 types of carbon-based materials, titanium-based compounds, alloy materials, metal compounds, and organic compounds. The specific capacity and rate capability of the carbon-based material need to be improved; the titanium-based compound has good structural performance and excellent rate performance, but has the defect of low specific capacity; alloy materials and metal compounds have higher theoretical specific capacity, but the cycle performance is poorer; the development of organic compounds is still in the beginning and needs to be studied intensively. Therefore, there is a need to develop a negative electrode material for sodium ion batteries with high energy, high power density, long cycle life, low cost, and high safety performance.
The industries of rare earth smelting, thermal power generation, semiconductor manufacturing and the like can generate a large amount of chlorine-containing wastewater, the dechlorination method which has the lowest cost and the simplest operation at present is a calcium-aluminum salt precipitation method, but waste residues generated by the precipitation method are not well treated and utilized at present. The key point of the chlorine-containing wastewater is to find a method for treating calcium-aluminum salt precipitation slag.
Disclosure of Invention
The invention provides an economical, environment-friendly and simple-operation method for preparing a sodium-ion battery cathode material with good cycle stability by converting waste residues of chlorine-containing wastewater treated by a calcium-aluminum salt precipitation method into a fluorine-type salt containing nickel, cobalt, manganese, aluminum and chlorine.
The purpose of the invention can be realized by the following technical scheme:
a preparation method of a sodium ion battery negative electrode material comprises the steps of adding a calcium source and an aluminum source into chlorine-containing waste liquid, stirring and reacting to obtain calcium-aluminum-fluorine salt, adding the calcium-aluminum-fluorine salt into a hydrochloric acid leaching liquid of a waste lithium ion battery, and carrying out an exchange reaction to obtain fluorine salt containing nickel, cobalt, manganese, aluminum and chlorine, namely the sodium ion battery negative electrode material.
The preparation method of the negative electrode material of the sodium-ion battery comprises the following steps:
(1) Adding chlorine-containing rare earth waste liquid (all chlorine-containing waste liquid can be used, and is not limited to rare earth smelting chlorine-containing waste liquid) into the stirring kettle a, adding a calcium source and an aluminum source, and continuously stirring for fully reacting to form suspension;
(2) Filtering the suspension to obtain dechlorinated solution which can be directly discharged; drying the obtained solid precipitate to obtain a fluorine salt containing calcium, aluminum and chlorine;
(3) Adding the anode material of the waste lithium ion battery into the stirring kettle b, adding hydrochloric acid, stirring and dissolving for a certain time, filtering, and removing filter residues to obtain hydrochloric acid leachate;
(4) Adding the solid obtained in the step (2) into a stirring kettle c according to the liquid-solid ratio of 50ml/g, adding the leachate obtained in the step (3), and stirring for reacting for a certain time;
(5) Filtering the suspension obtained in the step (4), and returning the filtrate to the step (4) for reaction; and drying the obtained filter residue to obtain the cobalt-nickel-manganese-aluminum-chlorine containing fluorine salt which is used as the cathode material of the sodium ion battery.
In the preparation method, the calcium source in the step (1) is calcium hydroxide, calcium oxide or calcium hydride; the aluminum source is sodium metaaluminate; the adding amount of the calcium and the aluminum is that the molar ratio of the calcium source to the aluminum source to the chloride ions in the waste liquid is 2-6.
In the preparation method, the reaction time in the steps (1) and (4) is 1-6 h, and the stirring speed is 150-450rpm.
In the preparation method, the drying temperature of the solid obtained in the steps (2) and (5) is 60-80 ℃, and the drying time is 5-12 h.
In the preparation method, the concentration of hydrochloric acid in the step (3) is 0.1 to 3mol/L.
Another object of the present invention is: the cathode material is a fluorine salt containing nickel, cobalt, manganese, aluminum and chlorine, and is prepared by the preparation method.
Compared with the prior art, the technical scheme of the invention has the following beneficial effects:
(1) The preparation method of the invention produces the cathode material of the sodium ion battery by using the waste residue generated by precipitating chloride ions in the chlorine-containing waste liquid by the calcium-aluminum salt method and valuable metals in the anode material of the waste lithium ion battery as raw materials, thereby not only recycling the dechlorination waste residue, but also recycling the valuable metals in the waste lithium ion battery.
(2) The preparation method of the negative electrode material of the sodium-ion battery is simple to operate, good in repeatability and good in commercial value.
(3) The sodium ion battery cathode material prepared by the preparation method has large specific capacity and good cycling stability.
Drawings
FIG. 1 is an XRD pattern of the material obtained in example 1;
FIG. 2 is a graph showing the spectral analysis of the material obtained in example 1;
FIG. 3 is a graph showing the charge and discharge curves of NiCoMnAl-Cl (OH) n/CaAl-Cl (OH) n material obtained in example 1 as a negative electrode material for a sodium ion battery;
FIG. 4 is a graph of the cycle performance of NiCoMnAl-Cl (OH) n/CaAl-Cl (OH) n material obtained in example 1 as a negative electrode material of a sodium ion battery.
Detailed Description
The present invention will be described in detail below with reference to the drawings and examples, but the present invention is not limited to the following examples.
Example 1
The preparation method of the negative electrode material of the sodium-ion battery comprises the following steps:
(1) Adding chlorine-containing rare earth waste liquid into a stirring kettle a, adding calcium hydroxide and sodium metaaluminate according to the molar ratio of the calcium hydroxide to the sodium metaaluminate to chloride ions being 4;
(2) Filtering the suspension to obtain dechlorinated solution which can be directly discharged; vacuum drying the obtained solid precipitate at 60 ℃ for 12h to obtain a fluorine salt containing calcium, aluminum and chlorine, which is marked as CaAl-Cl (OH) n;
(3) Adding a waste nickel cobalt lithium manganate battery cathode material into the stirring kettle b, adding 3mol/L hydrochloric acid, stirring for dissolving for 3 hours, filtering, and removing filter residues to obtain a hydrochloric acid leaching solution;
(4) Adding the solid obtained in the step (2) into a stirring kettle c according to the liquid-solid ratio of 50ml/g, adding the leachate obtained in the step (3), and stirring and reacting for 2 hours at 300 rpm;
(5) Filtering the suspension obtained in the step (4), and returning the filtrate to the step (4) for reaction; and drying the obtained filter residue at 60 ℃ for 12h to obtain a fluorine salt containing nickel, cobalt, manganese, aluminum and chlorine, which is marked as NiCoMnAl-Cl (OH) n/CaAl-Cl (OH) n and is used as a negative electrode material of the sodium-ion battery.
And (3) carrying out structural and morphological characterization on the sample by adopting an X-ray diffractometer and a scanning electron microscope, wherein the results are shown in a figure 1 and a figure 2. As can be seen from FIG. 1, the XRD pattern of CaAl-Cl (OH) n has obvious diffraction peaks, which shows that the material has better crystallization property, and the material pattern and Ca 2 Al(OH) 6 Cl.2H 2 O is close, which indicates that the material is hydroxide containing calcium, aluminum and chlorine; most of the diffraction peaks of NiCoMnAl-Cl (OH) n/CaAl-Cl (OH) n are consistent with those of CaAl-Cl (OH) n; in addition, the NiCoMnAl-Cl (OH) n/CaAl-Cl (OH) n material is subjected to element analysis, and the result shows that the product is producedThe product contained 8.58% of Ni,8.25% of Co,9.3% of Mn,5.76% of Al,1.86% of Ca,7.62% of Cl,.41.28% of O and 17.1% of H; scanning electron microscopy energy spectrum analysis is carried out on the NiCoMnAl-Cl (OH) n/CaAl-Cl (OH) n material (figure 2), and the nickel-cobalt-manganese is found to be uniformly distributed in the material, which shows that the NiCoMnAl-Cl (OH) n/CaAl-Cl (OH) n reserves the basic structure of CaAl-Cl (OH) n, and most of calcium is replaced by nickel, cobalt and manganese into the material crystal lattice.
In order to verify the electrical property of NiCoMnAl-Cl (OH) n/CaAl-Cl (OH) n used as the negative electrode material of the sodium-ion battery, niCoMnAl-Cl (OH) n/CaAl-Cl (OH) n is used as the negative electrode material to prepare the negative electrode sheet of the sodium-ion battery and the sodium-ion battery. Specifically, 60 mg of the NiCoMnAl-Cl (OH) N/CaAl-Cl (OH) N material prepared in example 1, 10 mg of a binder polyvinylidene fluoride (PVDF) and 30 mg of a conductive agent Super-P are mixed, uniformly ground, pulped by using N-methylpyrrolidone (NMP) as a solvent, coated on a copper foil, coated to a thickness of 100 μm, dried at 80 ℃ for 12 hours, rolled and cut into pieces, and the sodium-ion battery negative plate is obtained. A button cell is assembled in a glove box filled with argon by taking a pole piece containing NiCoMnAl-Cl (OH) n/CaAl-Cl (OH) n as a negative pole, taking a sodium piece as a positive pole and taking 1M sodium hexafluorophosphate (diethylene glycol dimethyl ether) as electrolyte. The electrochemical performance of the battery is measured, the charging and discharging curve is shown in figure 3, the cycle performance is shown in figure 4, and the result shows that the current density of the negative electrode material of the sodium-ion battery is 200 mAg -1 Has 333.76 mAhg in circulation -1 The initial specific capacity of the composite material is close to 100 percent of coulombic efficiency; after 500 times of circulation, the capacity of the product still has 310 mAhg -1 The cycle retention rate reaches 92.88%, and the cycle performance is stable.
Example 2
The preparation method of the negative electrode material of the sodium-ion battery comprises the following steps:
(1) Adding chlorine-containing waste liquid into a stirring kettle a, adding calcium hydride and sodium metaaluminate according to the molar ratio of the calcium hydride to the sodium metaaluminate to chloride ions being 5;
(2) Filtering the suspension to obtain dechlorinated solution which can be directly discharged; vacuum drying the obtained solid precipitate at 60 ℃ for 12h to obtain a fluorine salt containing calcium, aluminum and chlorine, and marking as CaAl-Cl (OH) n;
(3) Adding a waste lithium manganate battery anode material into the stirring kettle b, adding 1mol/L hydrochloric acid, stirring and dissolving for 3 hours, filtering, and removing filter residues to obtain a hydrochloric acid leaching solution;
(4) Adding the solid obtained in the step (2) into a stirring kettle c according to the liquid-solid ratio of 50ml/g, adding the leachate obtained in the step (3), and stirring and reacting for 4 hours at 150 rpm;
(5) Filtering the suspension obtained in the step (4), and returning the filtrate to the step (4) for reaction; and drying the obtained filter residue at 60 ℃ for 12h to obtain a fluorine salt containing manganese, aluminum and chlorine, which is marked as MnAl-Cl (OH) n/CaAl-Cl (OH) n and is used as a negative electrode material of the sodium-ion battery.
Elemental analysis of MnAl-Cl (OH) n/CaAl-Cl (OH) n material showed 17.3% Mn in the product, 5.96% Al,2.86% Ca and 7.23% Cl; the material is subjected to energy spectrum analysis by a scanning electron microscope, and manganese is uniformly distributed in the material, which indicates that the material retains the basic structure of CaAl-Cl (OH) n, and most of calcium is replaced by manganese and enters a material lattice.
The cathode plate of the sodium-ion battery and the sodium-ion battery are prepared by taking MnAl-Cl (OH) n/CaAl-Cl (OH) n as a cathode material. Specifically, 60 mg of the MnAl-Cl (OH) N/CaAl-Cl (OH) N material prepared in example 2, 10 mg of a binder polyvinylidene fluoride (PVDF) and 30 mg of a conductive agent Super-P were mixed, ground uniformly, pulped with N-methylpyrrolidone (NMP) as a solvent, coated on a copper foil, coated to a thickness of 100 μm, dried at 80 ℃ for 12 hours, rolled, and cut into pieces. A pole piece containing a material MnAl-Cl (OH) n/CaAl-Cl (OH) n is used as a negative pole, a sodium piece is used as a positive pole, 1M sodium hexafluorophosphate (diethylene glycol dimethyl ether) is used as electrolyte, and the button cell is assembled in a glove box filled with argon. The electrochemical performance of the battery is measured, and the result shows that the negative electrode material of the sodium-ion battery has the current density of 200 mAg -1 When circulating, has 330.5 mAhg -1 After the initial specific capacity is cycled for 400 times, the capacity retention rate reaches 91.28%, and the cycle performance is stable.
Example 3
The preparation method of the negative electrode material of the sodium-ion battery comprises the following steps:
(1) Adding chlorine-containing waste liquid into a stirring kettle a, adding calcium oxide and sodium metaaluminate according to the molar ratio of calcium oxide, sodium metaaluminate to chloride ions of 6.5;
(2) Filtering the suspension to obtain dechlorinated solution which can be directly discharged; vacuum drying the obtained solid precipitate at 50 ℃ for 8h to obtain a fluorine salt containing calcium, aluminum and chlorine, which is marked as CaAl-Cl (OH) n;
(3) Adding a waste lithium cobaltate battery positive electrode material into the stirring kettle b, adding 2mol/L hydrochloric acid, stirring and dissolving for 3 hours, filtering, and removing filter residues to obtain a hydrochloric acid leaching solution;
(4) Adding the solid obtained in the step (2) into a stirring kettle c according to the liquid-solid ratio of 50ml/g, adding the leachate obtained in the step (3), and stirring and reacting for 2 hours at 300 rpm;
(5) Filtering the suspension obtained in the step (4), and returning the filtrate to the step (4) for reaction; and drying the obtained filter residue at 80 ℃ for 5h to obtain cobalt-aluminum-chlorine-containing fluorine salt which is marked as CoAl-Cl (OH) n/CaAl-Cl (OH) n and is used as a negative electrode material of the sodium-ion battery.
Elemental analysis of the CoAl-Cl (OH) n/CaAl-Cl (OH) n material showed that the product contained 19.3% Co,6.01% Al,2.02% Ca and 6.89% Cl; scanning electron microscope energy spectrum analysis is carried out on the material, and cobalt is found to be uniformly distributed in the material, which indicates that the material retains the basic structure of CaAl-Cl (OH) n, and most of calcium is replaced by cobalt and enters the material crystal lattice.
The cathode piece of the sodium-ion battery and the sodium-ion battery are prepared by taking CoAl-Cl (OH) n/CaAl-Cl (OH) n as cathode materials. Specifically, 60 mg of the CoAl-Cl (OH) N/CaAl-Cl (OH) N material prepared in example 3 was mixed with 10 mg of polyvinylidene fluoride (PVDF) as a binder and 30 mg of Super-P as a conductive agent, uniformly ground, pulped with N-methylpyrrolidone (NMP) as a solvent, coated on a copper foil to a thickness of 100 μm, dried at 80 ℃ for 12 hours, rolled, and cut into pieces. Taking a pole piece containing a material CoAl-Cl (OH) n/CaAl-Cl (OH) n as a negative pole, a sodium piece as a positive pole, 1M sodium hexafluorophosphate (diethylene glycol dimethyl ether) as electrolyte, and filling argonThe glove box is assembled into a button cell. The electrochemical performance of the battery is measured, and the result shows that the negative electrode material of the sodium-ion battery has the current density of 200 mAg -1 Has 336.5 mAhg in circulation -1 After the initial specific capacity is cycled for 500 times, the capacity retention rate reaches 94.45%, and the cycle performance is stable.
Claims (7)
1. A preparation method of a sodium ion battery negative electrode material is characterized by comprising the following steps: adding a calcium source and an aluminum source into chlorine-containing waste liquid, stirring and reacting to obtain calcium-aluminum-fluorine salt, adding the calcium-aluminum-fluorine salt into a hydrochloric acid leachate of a waste lithium ion battery anode material, and carrying out an exchange reaction to obtain fluorine salt containing nickel, cobalt, manganese, aluminum and chlorine, namely the sodium ion battery anode material;
the method specifically comprises the following steps:
(1) Adding chlorine-containing waste liquid into a stirring kettle a, adding a calcium source and an aluminum source, and continuously stirring for fully reacting to form suspension;
(2) Filtering the suspension to obtain dechlorinated solution which can be directly discharged; drying the obtained solid precipitate to obtain a fluorine salt containing calcium, aluminum and chlorine;
(3) Adding the anode material of the waste lithium ion battery into the stirring kettle b, adding hydrochloric acid, stirring and dissolving for a certain time, filtering, and removing filter residues to obtain hydrochloric acid leachate;
(4) Adding the solid obtained in the step (2) into a stirring kettle c according to the liquid-solid ratio of 50ml/g, adding the leachate obtained in the step (3), and stirring for reacting for a certain time;
(5) Filtering the suspension obtained in the step (4), and returning the filtrate to the step (4) for reaction; and drying the obtained filter residue to obtain a fluorine salt containing nickel, cobalt, manganese, aluminum and chlorine, which is used as a negative electrode material of the sodium ion battery.
2. The method for preparing the negative electrode material of the sodium-ion battery according to claim 1, wherein: the calcium source in the step (1) is calcium hydroxide, calcium oxide or calcium hydride;
the aluminum source is sodium metaaluminate;
the adding amount of the calcium and the aluminum is added according to the molar ratio of the calcium source to the aluminum source to the chloride ions in the waste liquid being 2-6.
3. The method for preparing the negative electrode material of the sodium-ion battery according to claim 2, characterized in that: the adding amount of the calcium and the aluminum is in a proportion of 4.
4. The method for preparing the negative electrode material of the sodium-ion battery according to claim 1, wherein: the reaction time in the steps (1) and (4) is 1-6 h, and the stirring speed is 150-450rpm.
5. The preparation method of the negative electrode material of the sodium-ion battery as claimed in claim 1, characterized in that: and (3) drying the solid obtained in the step (2) and the step (5) at the temperature of between 60 and 80 ℃ for 5 to 12 hours.
6. The preparation method of the negative electrode material of the sodium-ion battery as claimed in claim 1, characterized in that: the concentration of hydrochloric acid in the step (3) is 0.1 to 3mol/L.
7. A negative electrode material for a sodium ion battery, characterized in that: the material is a fluorine type salt containing nickel cobalt manganese aluminum chloride, and is prepared by the preparation method of any one of claims 1 to 6.
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