CN115275193A - Sulfur-containing lithium battery positive electrode material, preparation method thereof and lithium battery - Google Patents
Sulfur-containing lithium battery positive electrode material, preparation method thereof and lithium battery Download PDFInfo
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 102
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 102
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 77
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 77
- 239000011593 sulfur Substances 0.000 title claims abstract description 77
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000011572 manganese Substances 0.000 claims abstract description 53
- 239000010406 cathode material Substances 0.000 claims abstract description 39
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 36
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 36
- 150000001450 anions Chemical class 0.000 claims abstract description 18
- 125000000129 anionic group Chemical group 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 17
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 16
- 239000007791 liquid phase Substances 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 8
- 229910016612 MnaNibCoc Inorganic materials 0.000 claims abstract description 6
- 239000000126 substance Substances 0.000 claims abstract description 6
- 229910052751 metal Inorganic materials 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 21
- 239000010405 anode material Substances 0.000 claims description 17
- 239000003792 electrolyte Substances 0.000 claims description 7
- 239000012071 phase Substances 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 239000006104 solid solution Substances 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 2
- 239000007773 negative electrode material Substances 0.000 claims description 2
- 125000000101 thioether group Chemical group 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 239000013078 crystal Substances 0.000 abstract description 4
- 230000009467 reduction Effects 0.000 abstract description 4
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- 150000002641 lithium Chemical class 0.000 abstract description 2
- 238000013508 migration Methods 0.000 abstract description 2
- 230000005012 migration Effects 0.000 abstract description 2
- 238000005245 sintering Methods 0.000 abstract description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 21
- 239000000463 material Substances 0.000 description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 9
- 229910052760 oxygen Inorganic materials 0.000 description 9
- 239000001301 oxygen Substances 0.000 description 9
- 229920000447 polyanionic polymer Polymers 0.000 description 7
- 239000000203 mixture Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 229910008514 Li1.2Mn0.54Ni0.13Co0.13O2 Inorganic materials 0.000 description 3
- 229910002983 Li2MnO3 Inorganic materials 0.000 description 3
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- 230000000052 comparative effect Effects 0.000 description 3
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
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- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- YASYEJJMZJALEJ-UHFFFAOYSA-N Citric acid monohydrate Chemical compound O.OC(=O)CC(O)(C(O)=O)CC(O)=O YASYEJJMZJALEJ-UHFFFAOYSA-N 0.000 description 1
- 229910012820 LiCoO Inorganic materials 0.000 description 1
- 229910001228 Li[Ni1/3Co1/3Mn1/3]O2 (NCM 111) Inorganic materials 0.000 description 1
- 229910003870 O—Li Inorganic materials 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
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- 229960002303 citric acid monohydrate Drugs 0.000 description 1
- ZBYYWKJVSFHYJL-UHFFFAOYSA-L cobalt(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Co+2].CC([O-])=O.CC([O-])=O ZBYYWKJVSFHYJL-UHFFFAOYSA-L 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
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- 239000008367 deionised water Substances 0.000 description 1
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- 150000002500 ions Chemical class 0.000 description 1
- KEQHHFKPFQFWAJ-UHFFFAOYSA-M lithium;acetate;hydrate Chemical compound [Li+].O.CC([O-])=O KEQHHFKPFQFWAJ-UHFFFAOYSA-M 0.000 description 1
- 229940082328 manganese acetate tetrahydrate Drugs 0.000 description 1
- CESXSDZNZGSWSP-UHFFFAOYSA-L manganese(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Mn+2].CC([O-])=O.CC([O-])=O CESXSDZNZGSWSP-UHFFFAOYSA-L 0.000 description 1
- 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 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229940078487 nickel acetate tetrahydrate Drugs 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- OINIXPNQKAZCRL-UHFFFAOYSA-L nickel(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Ni+2].CC([O-])=O.CC([O-])=O OINIXPNQKAZCRL-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 1
- 229940048181 sodium sulfide nonahydrate Drugs 0.000 description 1
- WMDLZMCDBSJMTM-UHFFFAOYSA-M sodium;sulfanide;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Na+].[SH-] WMDLZMCDBSJMTM-UHFFFAOYSA-M 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
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- -1 sulfate compound Chemical class 0.000 description 1
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- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 description 1
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
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- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- 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
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Abstract
The invention discloses a sulfur-containing lithium battery cathode material, a preparation method thereof and a lithium battery. The positive electrode material of the sulfur-containing lithium battery is a lithium-rich manganese-based positive electrode material doped with anionic sulfur and has a chemical formula of Li1+δMnaNibCocSxOyWherein δ = 0-0.2, a = 0.45-0.7, b = 0.05-0.35, c = 0.05-0.3, x = 0.001-0.1, y = 1.9-1.999, and x + y =2, δ + a + b + c =1; the cathode material which is not doped with sulfur is prepared by fully reacting and drying in a solution containing anionic sulfur through a liquid phase method. The positive electrode material of the present inventionIn the method, as the anion sulfur has a tighter chemical bond and a larger crystal lattice with the metal binding capacity, more stable anion redox and faster lithium ion migration capacity are realized, and finally the modified lithium-rich manganese-based cathode material has high cycle stability and rate capability. In addition, the liquid phase method adopted by the invention is simple in sulfur element doping synthesis step, easy to operate, free of sintering at high temperature, and has the advantages of large-scale production capacity and energy conservation and emission reduction.
Description
Technical Field
The invention relates to the technical field of lithium batteries, in particular to a sulfur-containing lithium battery positive electrode material, a preparation method thereof and a lithium battery.
Background
Global energy crisis and increasing environmental pollution have necessitated the development of clean energy-based grid storage, vehicles, and portable devices. As a clean energy, the novel lithium ion battery has the advantages of high safety, good cyclicity, long service life, environmental friendliness, recoverability and the like.
Lithium ion batteries typically include an anode, a cathode, a separator, and an electrolyte. Lithium ion batteries typically have a carbon negative electrode (or anode) and a transition metal oxide positive electrode (or cathode). The cathode and anode are generally layered structures to contain lithium ions that are transferred between the cathode and anode for energy transfer during charging and discharging.
The cathode material, as an important component of a lithium ion battery, is a key factor for determining the safety, capacity and price of the battery. In terms of price, in the lithium ion batteries produced commercially at present, the cost of the anode material accounts for about 20% -40% of the total cost of the batteries, and the reduction of the price of the anode material directly determines the reduction of the price of the lithium ion batteries, especially the power lithium ion batteries applied to new energy vehicles. In addition, lithium ion batteries, especially power lithium ion batteries, have special requirements in the aspects of large-current discharge, specific energy, safety and the like, and the currently researched or applied positive electrode materials do not completely meet the requirements, so the development of the lithium ion power batteries is greatly restricted.
The positive electrode of the first generation lithium ion battery was lithium cobaltate (LiCoO)2) This is a layered compound, the oxygen atoms are formed in a close-packed form, and this structure forms octahedral voids corresponding to the number of oxygen atoms. The transition metal layers and the lithium layers are alternately arranged in the structure. Lithium cobaltate is weak in high voltage stability, and when half of lithium is removed from lithium cobaltate (voltage higher than 4.3V), the layered compound becomes unstable due to oxygen loss. Cobalt is expensive, which increases the cost of lithium cobaltate. By adding nickel and manganese elements, the performance and the cost are further optimized. Such an optimized positive electrode material is called a ternary material (NCM).
The first ternary material was LiNi1/3Co1/3Mn1/3O2(NCM 333). In order to increase the capacity, the improvement of the structure and the components of the ternary material is divided into two directions, namely, the nickel content is improved, the cobalt content is reduced, and the stability of a laminated structure is increased; another is to increase the relative amounts of lithium and manganese, such as lithium-rich manganese-based materials proposed in argon national laboratory (Argonne national Lab). The material has lithium in the transition metal layer to form a lithium-rich phase, and the lithium-rich phase and the non-lithium-rich phase form an atomic solid solution or a nano two-phase structure. This material has the general formula x LiMO2-(1-x)Li2MnO3Wherein 0 is<x<1, and wherein M is one or more ions.
The properties of the lithium-rich manganese-based positive electrode material are related to its composition, in particular to Li2MnO3The content of (c) is related. High Li2MnO3The composition may lead to higher capacity due to the introduction of Li-O-Li configuration in the material and the redox of oxygen. However, the redox of oxygen brings irreversible oxygen release and side reaction with the electrolyte, resulting in a decrease in coulombic efficiency, a decline in stability, a decline in voltage, and poor rate capability, etc., resulting in failure to commercialize it in late time. Therefore, the lithium-rich manganese-based material with stability and high multiplying power is urgently needed to be provided.
Proper anion sulfur doping to replace lattice oxygen site can inhibit the irreversible degree of oxygen oxidation reduction in the material, increase lattice spacing, raise conductivity, etc. and thus raise the specific capacity density and rate performance of the positive electrode material. However, doping of the anions of sulfur is experimentally difficult to achieve due to the readily oxidizable nature of the anion sulfur. The existing sulfur-containing cathode material is mainly characterized in that polyanion groups of sulfur are doped into a crystal lattice phase and the surface, wherein the sulfur is positive valence. The sulfate ions can inhibit the contact of the material and electrolyte, reduce side reactions and improve the conductivity of the material, thereby improving the stability and the rate capability to a certain extent. For example, kang et al doped nickel sulfate in lithium rich materials, 250-cycle stability at 1C was about 78% (ACS appl. Mater. Interfaces 2020,12, 13996-14004). Zhang et al constructed surface oxygen vacancies by forming Mn sulfate compound on the surface, and the voltage declined to 2.77V after 200 cycles, which is improved compared with 2.48V declined from the original material (ACS appl. Mater. Interfaces 2020,12,38, 42660-42668). However, the sulfur-containing positive electrodes are doped and coated by positive-valence polyanion based on sulfur, and sulfur is not doped into crystal lattices in the form of negative-valence anions, so that the modification effect on positive electrode materials is limited. On the other hand, polyanionic sulfate does not have redox activity by itself, and causes a loss of capacity of the positive electrode material. Based on the above existing sulfur-containing cathode materials, there is no report of an anionic sulfur-doped lithium-rich cathode material.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a sulfur-containing lithium battery cathode material with high energy density and high discharge capacity in the battery charging and discharging process. In the technical scheme of the invention, sulfur is doped into the anode material as anions, and through the enhancement of the covalent interaction of the anions and metal, on one hand, the activity of oxygen oxidation reduction is inhibited, the side reaction of an interface is reduced, and the cycle stability and the high-temperature stability of the anode material are greatly improved; on the other hand, due to the large-size effect of the anionic sulfur, the rate capability of the cathode material is remarkably improved.
The invention also aims to provide a method for preparing the lithium battery cathode material.
The invention also provides a lithium battery containing the lithium battery cathode material. The lithium battery based on the sulfur-containing cathode material has good cycle performance and high rate.
The purpose of the invention is realized by the following technical scheme.
A sulfur-containing lithium battery anode material is a lithium-rich manganese-based sulfur-doped anode material with a chemical formula of Li1+δMnaNibCocSxOyWherein δ =0 to 0.2, a =0.45 to 0.7, b =0.05 to 0.35, c =0.05 to 0.3, x =0.001 to 0.1, y =1.9 to 1.999, and x + y =2, δ + a + b + c =1; wherein sulfur is anionic (S)n-) In the form of a materialAnd (4) medium doping. The sulfur-containing cathode material is prepared by fully reacting an undoped sulfur-containing cathode material in a solution containing anionic sulfur by a liquid phase method and drying.
In the positive electrode material of the sulfur-containing lithium battery, sulfur is in the form of anion Sn-Exist, in many cases, 0<n≤2。
Preferably, the sulfur-containing lithium battery cathode material Li1+δMnaNibCocSxOyδ =0 to 0.2, a =0.45 to 0.7, b =0.05 to 0.35, c =0.05 to 0.3, x =0.001 to 0.05, and y =1.95 to 1.999.
Preferably, a two-phase solid solution or a nano-mixture, namely zLiMO, is formed in the sulfur-containing lithium battery cathode materialyS2-y-(1-z)Li2MnOyS2-yWherein 0 is<z<1,m is a combination of metal elements including Ni, co, mn higher than 2+ valence, and y =1.9 to 1.999.
Preferably, the sulfur-containing lithium battery positive electrode material is charged and discharged under the conditions of 30 ℃, 2.1-4.8V and 0.1C, and the discharge capacity is more than 300mAh/g.
Preferably, the lithium battery anode material is charged and discharged under the conditions of 30 ℃, 2.1-4.8V and 1C, and the discharge capacity is more than 80% of the discharge capacity of 0.1C.
The invention also provides a preparation method of the sulfur-containing lithium battery anode material, which comprises the steps of adding the lithium-rich manganese-based lithium battery anode material into a solution containing anionic sulfur to perform liquid phase reaction, uniformly stirring, filtering to obtain the sulfur-containing lithium battery anode material, and drying in vacuum.
In the above preparation method, the solution containing anionic sulfur is obtained by dissolving a soluble salt of sulfur in a solvent, wherein the soluble salt of sulfur is preferably a sulfide, including but not limited to anhydrous sodium sulfide, sodium sulfide nonahydrate, thiourea, thioacetamide, etc.; the solvent comprises one or more of water and ethanol.
Preferably, the concentration of the solution containing anionic sulfur is 0.01mol/L to 0.5mol/L, and the anionic sulfur can be S2-And the like.
In the preparation method, the general formula of the lithium-rich manganese-based lithium battery positive electrode material is Li1+δMnaNibCocO2Wherein δ =0 to 0.2, a =0.45 to 0.7, b =0.05 to 0.35, c =0.05 to 0.3, and δ + a + b + c =1.
Preferably, the concentration range of the positive electrode material of the lithium-rich manganese-based lithium battery in the solution containing the anionic sulfur is 0.002-0.01 g/mL.
Preferably, the stirring speed of the liquid phase reaction is 300-500 rpm, the reaction temperature is 30-40 ℃, and the time is 0.5-1 hour.
Preferably, the temperature of the vacuum drying is 100-150 ℃, and the drying time is 12-24 h.
The invention also provides a lithium ion battery which comprises a positive electrode material, a negative electrode material, a diaphragm and an electrolyte, wherein the positive electrode material is the sulfur-containing lithium battery positive electrode material.
Compared with the prior art, the invention has the following advantages and beneficial effects:
the invention dopes sulfur element in the lithium-rich manganese-based anode material by a liquid phase method for the first time, and realizes sulfur doping in an anion form. Compared with the existing sulfur-containing cathode material, the lithium-rich manganese-based cathode material with the anion sulfur is synthesized by the method. The anion sulfur has a chemical bond with a relatively tight metal binding capacity and a relatively large crystal lattice, so that more stable anion redox and faster lithium ion migration capacity are realized, and finally the modified lithium-rich manganese-based positive electrode material has high cycle stability and rate capability. In addition, the liquid phase method adopted by the invention is simple in sulfur element doping synthesis step, easy to operate, free of sintering synthesis at high temperature, and has the advantages of large-scale production capacity and energy conservation and emission reduction.
Drawings
Fig. 1 is a charge-discharge graph of a half-cell based on the lithium-rich manganese-based positive electrode materials prepared in examples 1 and 2.
Fig. 2 is a graph of half-cell charge-discharge cycles based on the lithium-rich manganese-based positive electrode materials prepared in example 1 and example 2.
Fig. 3 is a graph of charge and discharge rate performance of half-cells based on the lithium-rich manganese-based positive electrode materials prepared in examples 1 and 2.
Fig. 4 is a graph of high temperature cycling performance of half cells based on the lithium-rich manganese-based positive electrode materials prepared in examples 1 and 2.
Fig. 5 is a graph showing charge and discharge cycles of a half cell based on the lithium-rich manganese-based positive electrode material having a sulfur doping amount of 0.04at% prepared in example 3.
Fig. 6 is a comparative plot of charge-discharge cycle curves for half-cells based on the anionic sulfur-containing cathode material prepared in example 2 and the polyanion sulfate doped lithium-rich manganese-based cathode material prepared in comparative examples.
Detailed Description
The technical solutions of the present invention are described in further detail below with reference to the detailed description and the accompanying drawings, but the scope and the embodiments of the present invention are not limited thereto. The experimental procedures, in which specific conditions are not specified in the examples, are generally carried out under conventional conditions or under conditions recommended by the manufacturers. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
The performance of the cathode material prepared in the example was measured by preparing a button cell;
the electrochemical performance of the positive electrode material is embodied by a button-type half cell. The half-cell positive electrode is prepared by mixing the following positive electrode materials: conductive agent (Super P): binder (PVDF) at 80:10:10 in mass ratio.
The procedure for preparing the half-cell positive electrode was as follows: the positive electrode material was mixed with Super P, polyvinylidene fluoride PVDF to form a homogeneous powder mixture. The powder mixture was added to NMP and mixed to form a slurry. The slurry was applied to an aluminum foil current collector to form a thin film. The coated positive electrode was dried under vacuum at 90 ℃ for 6 hours to remove NMP. The dried aluminum foil coated with the positive electrode material was then cut into disks, rolled, weighed, dried overnight at 110 ℃ in a vacuum oven, and finally transferred to an argon-filled glove box.
Preparing a button type lithium battery: the prepared positive electrode is used as a positive electrode of a lithium battery, and a lithium sheet is used as a negative electrode. The electrolyte is LB-372 type high voltage electrolyte from multi-reagent company. The membrane was a Whatman glass fiber membrane.
Example 1
Sulfur-free doped lithium-rich manganese-based positive electrode material Li1.2Mn0.54Ni0.13Co0.13O2The preparation method comprises the following specific steps:
(1) According to the stoichiometric ratio of each element component in the chemical formula, 2.5709g of lithium acetate monohydrate (5% excess), 0.6470g of nickel acetate tetrahydrate, 0.6476g of cobalt acetate tetrahydrate and 2.6470g of manganese acetate tetrahydrate are dissolved in 300mL of deionized water, and 4.9656g of ethylene glycol and 8.4056g of citric acid monohydrate are added to obtain a mixed solution;
(2) Evaporating the mixed solution to a gel state in a rotary evaporator;
(3) Drying the obtained gel in a vacuum oven at 150 ℃ for 6h, and removing water;
(4) Grinding the obtained dry gel into powder, preserving heat for 4h at 450 ℃ in a tubular furnace in air atmosphere, reacting for 12h at 900 ℃, and cooling along with the furnace to obtain the lithium-rich manganese-based anode material Li1.2Mn0.54Ni0.13Co0.13O2。
The obtained lithium-rich manganese-based cathode material Li1.2Mn0.54Ni0.13Co0.13O2The R2032 type button half-cell is assembled, the charge and discharge test is carried out under the conditions of 30 ℃, 2.1-4.8V and 0.1C, the charge and discharge curve is as the charge and discharge curve of the sample S0 in figure 1, and the discharge capacity is 300mAh/g as can be seen from figure 1.
Example 2
Lithium-rich cathode material Li doped with anion sulfur by liquid phase method1.2Mn0.54Ni0.13Co0.13O1.998S0.002The preparation method comprises the following specific steps:
using the lithium-rich manganese-based positive electrode material prepared in example 1, 0.01mol/L Na was added thereto2In the S solution, the proportion of the anode material to the solution is 4g/L, the mixture is stirred for 30 minutes at the rotating speed of 400rpm, filtered, dried in a vacuum oven at 120 ℃ for 12 hours to obtain the lithium-rich anodeMaterial Li1.2Mn0.54Ni0.13Co0.13O1.998S0.002。
The obtained lithium-rich manganese-based cathode material Li1.2Mn0.54Ni0.13Co0.13O1.998S0.002The R2032 type button half-cell is assembled, the charge and discharge test is carried out under the conditions of 30 ℃, 2.1-4.8V and 0.1C, the charge and discharge curve is as the charge and discharge curve of the sample S1 in the figure 1, the discharge capacity is 305mAh/g as can be known from the figure 1, and compared with the sample S0 of the lithium-rich anode material which is not doped with sulfur in the embodiment 1, the discharge capacity is further improved.
The obtained lithium-rich manganese-based cathode material Li1.2Mn0.54Ni0.13Co0.13O1.998S0.002An R2032 type button half cell is assembled, and a charge-discharge test is carried out under the conditions of 30 ℃, 2.1-4.8V and 1C, and the cycle performance is shown as a sample S1 in figure 2. The cycling performance of sample S0 in fig. 2 was tested under the same conditions with the sulfur-undoped lithium-rich positive electrode material of example 1. Li relative to the S0 sample in FIG. 21.2Mn0.54Ni0.13Co0.13O1.998S0.002The cycle life of the lithium-rich manganese-based positive electrode material is obviously prolonged.
The obtained lithium-rich manganese-based cathode material Li1.2Mn0.54Ni0.13Co0.13O1.998S0.002The R2032 type button half-cell is assembled and the multiplying power performance test is carried out under the conditions of 30 ℃ and 2.1-4.8V, such as S1 in figure 3. The rate capability of sample S0 in fig. 3 was tested under the same conditions with the sulfur-undoped lithium-rich cathode material of example 1. Li relative to the S0 sample in FIG. 31.2Mn0.54Ni0.13Co0.13O1.998S0.002The multiplying power performance 1C exceeds 240mAh/g, and is obviously improved.
The obtained lithium-rich manganese-based cathode material Li1.2Mn0.54Ni0.13Co0.13O1.998S0.002Assembled into an R2032 type button half cell, and subjected to cycle performance test at 55 ℃, 2.1-4.8V and 1C, as shown in figure 4And S1. The high temperature performance of sample S0 in fig. 4 was tested under the same conditions with the sulfur-undoped lithium-rich positive electrode material of example 1. Li relative to the S0 sample in FIG. 41.2Mn0.54Ni0.13Co0.13O1.998S0.002The high-temperature cycle performance of the alloy still exceeds 250mAh/g within 50 circles, and the stability is obviously improved.
Example 3
Lithium-rich cathode material Li doped with anion sulfur by liquid phase method1.2Mn0.54Ni0.13Co0.13O1.996S0.004The preparation method comprises the following specific steps:
using the lithium-rich manganese-based positive electrode material prepared in example 1, 0.02mol/L Na was added2In the S solution, the proportion of the positive electrode material to the solution is 4g/L, the solution is stirred for 30 minutes at the rotating speed of 400rpm, filtered, dried in a vacuum oven at 120 ℃ for 12 hours to obtain the lithium-rich positive electrode material Li1.2Mn0.54Ni0.13Co0.13O1.998S0.004。
The obtained lithium-rich manganese-based cathode material Li1.2Mn0.54Ni0.13Co0.13O1.998S0.004The R2032 type button half-cell is assembled, and the charge and discharge test is carried out under the conditions of 30 ℃, 2.1-4.8V and 1C, and the cycle performance is shown in figure 5. As can be seen from FIG. 5, the capacity of 200mAh/g is still obtained after 200 cycles of circulation, and the circulation performance is good.
Comparative example
Polyanion sulfate radical doped lithium-rich cathode material Li1.2Mn0.54Ni0.13Co0.13O1.992(SO4)0.002The preparation method comprises the following specific steps:
(1) Using the lithium-rich manganese-based positive electrode material prepared in example 1, 0.01mol/L Na was added thereto2In the S solution, the proportion of the positive electrode material to the solution is 4g/L, the solution is stirred for 30 minutes at the rotating speed of 400rpm, filtered, dried for 12 hours at the temperature of 120 ℃ in a vacuum oven to obtain the lithium-rich positive electrode material Li1.2Mn0.54Ni0.13Co0.13O1.998S0.002。
(2) The obtained lithium-rich manganese-based cathode material Li1.2Mn0.54Ni0.13Co0.13O1.998S0.002Introducing oxygen into a muffle furnace, heating to 300 ℃ for 5 hours to fully oxidize the sulfur element to prepare the polyanion sulfate radical doped lithium-rich cathode material Li1.2Mn0.54Ni0.13Co0.13O1.992(SO4)0.002。
(3) The obtained polyanion sulfate radical-doped lithium-rich cathode material is assembled into an R2032 type button half-cell, and a charge-discharge test is carried out at 30 ℃, 2.1-4.8V and 1C, and the cycle performance is compared with that of the embodiment 2, as shown in figure 6. As can be seen from fig. 6, the cycle of the cathode material doped with the liquid-phase anion sulfur is significantly more stable than that of the polyanion sulfate-doped lithium-rich cathode material.
The above embodiments are merely preferred embodiments of the present invention, and the technical solutions of the present invention are described in further detail, but the scope and the embodiments of the present invention are not limited thereto, and any changes, combinations, deletions, substitutions or modifications that do not depart from the spirit of the invention are included in the scope of the present invention.
Claims (10)
1. A sulfur-containing lithium battery anode material is a lithium-rich manganese-based sulfur-doped anode material with a chemical formula of Li1+δMnaNibCocSxOyWherein δ =0 to 0.2, a =0.45 to 0.7, b =0.05 to 0.35, c =0.05 to 0.3, x =0.001 to 0.1, y =1.9 to 1.999, and x + y =2, δ + a + b + c =1; the sulfur is doped in the cathode material in an anion form, and the sulfur-containing lithium battery cathode material is obtained by fully reacting the cathode material which is not doped with sulfur in a solution containing anion sulfur through a liquid phase method and drying.
2. The positive electrode material for a sulfur-containing lithium battery as claimed in claim 1, wherein δ =0 to 0.2, a =0.45 to 0.7, b =0.05 to 0.35, c =0.05 to 0.3, x =0.001 to 0.05, and y =1.95 to 1.999.
3. The positive electrode material for sulfur-containing lithium batteries according to claim 1, wherein a two-phase solid solution or a nano-hybrid, namely zLiMO, is formed in the positive electrode material for sulfur-containing lithium batteriesyS2-y-(1-z)Li2MnOyS2-yWherein 0 is<z<1,m is a combination of metal elements including Ni, co, mn higher than 2+ valence, and y =1.9 to 1.999.
4. The positive electrode material of the sulfur-containing lithium battery as claimed in claim 1, wherein the positive electrode material of the sulfur-containing lithium battery is charged and discharged at 30 ℃ under the conditions of 2.1-4.8V and 0.1C, and the discharge capacity is greater than 300mAh/g; the discharge capacity is more than 80% of the discharge capacity at 0.1C when the charge and discharge are carried out at 30 ℃ under the conditions of 2.1-4.8V and 1C.
5. The method for preparing the positive electrode material of the sulfur-containing lithium battery as claimed in any one of claims 1 to 4, wherein the positive electrode material of the lithium-rich manganese-based lithium battery is prepared by adding a solution containing anionic sulfur into the positive electrode material of the lithium-rich manganese-based lithium battery to perform a liquid phase reaction, uniformly stirring, filtering to obtain the positive electrode material of the sulfur-containing lithium battery, and drying in vacuum1+δMnaNibCocO2，δ＝0～0.2，a＝0.45～0.7，b＝0.05～0.35，c＝0.05～0.3，δ+a+b+c＝1。
6. The method according to claim 5, wherein the solution containing anionic sulfur is a solution obtained by dissolving a soluble salt of sulfur in a solvent.
7. The method of claim 6, wherein the soluble salt of sulfur is a sulfide.
8. The method according to claim 5, wherein the concentration of the solution containing anionic sulfur is 0.01 to 0.5mol/L, and the anionic sulfur is S2-。
9. The preparation method according to claim 5, wherein the concentration of the lithium-rich manganese-based lithium battery positive electrode material in the solution containing the anionic sulfur is in the range of 0.002 to 0.01g/mL; the stirring speed of the liquid phase reaction is 300-500 rpm, the reaction temperature is 30-40 ℃, and the time is 0.5-1 hour; the temperature of vacuum drying is 100-150 ℃, and the drying time is 12-24 h.
10. A lithium ion battery, comprising a positive electrode material, a negative electrode material, a separator and an electrolyte, wherein the positive electrode material is the sulfur-containing lithium battery positive electrode material of any one of claims 1 to 4.
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| CN109148856A (en) * | 2018-08-24 | 2019-01-04 | 南开大学 | A kind of preparation method of high circulation capacity reactance voltage decline lithium-rich positive electrode |
| CN111370686A (en) * | 2020-03-20 | 2020-07-03 | 昆明理工大学 | Anion-cation co-doped modified lithium-rich manganese composite cathode material and preparation method thereof |
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