CN114956020A - Li 3 Preparation method of P crystal powder and Li 3 P crystal powder and application thereof - Google Patents
Li 3 Preparation method of P crystal powder and Li 3 P crystal powder and application thereof Download PDFInfo
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- 239000000843 powder Substances 0.000 title claims abstract description 62
- 239000013078 crystal Substances 0.000 title claims abstract description 61
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 105
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 97
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 claims abstract description 38
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000007787 solid Substances 0.000 claims abstract description 25
- 238000001035 drying Methods 0.000 claims abstract description 12
- 239000011261 inert gas Substances 0.000 claims abstract description 12
- 238000006138 lithiation reaction Methods 0.000 claims abstract description 12
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- 238000005406 washing Methods 0.000 claims abstract description 8
- 238000003756 stirring Methods 0.000 claims abstract description 7
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 27
- 229910001416 lithium ion Inorganic materials 0.000 claims description 27
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 21
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 20
- 239000003795 chemical substances by application Substances 0.000 claims description 19
- 239000013589 supplement Substances 0.000 claims description 17
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 14
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 14
- 229910052751 metal Inorganic materials 0.000 claims description 12
- 239000002184 metal Substances 0.000 claims description 12
- 229910052786 argon Inorganic materials 0.000 claims description 10
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 10
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- XJKSTNDFUHDPQJ-UHFFFAOYSA-N 1,4-diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=C(C=2C=CC=CC=2)C=C1 XJKSTNDFUHDPQJ-UHFFFAOYSA-N 0.000 claims description 3
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- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 3
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 3
- 239000001307 helium Substances 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- 229930184652 p-Terphenyl Natural products 0.000 claims description 3
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 3
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
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- 229910052698 phosphorus Inorganic materials 0.000 description 4
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- FFJFXCFOFFTFDK-UHFFFAOYSA-N 1,1'-biphenyl oxolane Chemical compound O1CCCC1.C1=C(C=CC=C1)C1=CC=CC=C1 FFJFXCFOFFTFDK-UHFFFAOYSA-N 0.000 description 2
- -1 4, 4' -dimethyl diphenyl lithium Chemical compound 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910018068 Li 2 O Inorganic materials 0.000 description 2
- 229910018071 Li 2 O 2 Inorganic materials 0.000 description 2
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- 229910000103 lithium hydride Inorganic materials 0.000 description 2
- PDZGAEAUKGKKDE-UHFFFAOYSA-N lithium;naphthalene Chemical compound [Li].C1=CC=CC2=CC=CC=C21 PDZGAEAUKGKKDE-UHFFFAOYSA-N 0.000 description 2
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- CBCOKTYDIMEMMH-UHFFFAOYSA-N 1,1'-biphenyl;lithium Chemical compound [Li].[Li].C1=CC=CC=C1C1=CC=CC=C1 CBCOKTYDIMEMMH-UHFFFAOYSA-N 0.000 description 1
- GBVSONMCEKNESD-UHFFFAOYSA-N 1,1'-biphenyl;lithium Chemical compound [Li].C1=CC=CC=C1C1=CC=CC=C1 GBVSONMCEKNESD-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- 102000004310 Ion Channels Human genes 0.000 description 1
- 229910018091 Li 2 S Inorganic materials 0.000 description 1
- 229910012820 LiCoO Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
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- 238000004364 calculation method Methods 0.000 description 1
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- 238000012986 modification Methods 0.000 description 1
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- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 description 1
- 238000010200 validation analysis Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/08—Other phosphides
- C01B25/081—Other phosphides of alkali metals, alkaline-earth metals or magnesium
-
- 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
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
-
- 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
- H01M4/5805—Phosphides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
-
- 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
-
- 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
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses Li 3 The preparation method of the P crystal powder comprises the following steps: s1, removing oxide on the surfaces of red phosphorus and lithium to obtain pretreated red phosphorus and pretreated lithium, and storing in inert gas for later use; s2, dissolving the polycyclic aromatic hydrocarbon into an organic solvent to prepare polycyclic aromatic hydrocarbon organic solution; s3, dissolving the pretreated lithium prepared in the step S1 into the polycyclic aromatic hydrocarbon organic solution prepared in the step S2 to prepare a lithiated solution; s4, adding the pretreated red phosphorus prepared in the step S1 into the lithiation solution prepared in the step S3, and fully stirring to obtain a mixture(ii) a S5, centrifugally separating solid powder from the mixture prepared in the step S4, washing and drying to obtain powder; s6, roasting and crushing the powder prepared in the step S5 to obtain Li 3 P crystal powder. The method has the advantages of cheap and easily-obtained raw materials, simple process, safe production, high product purity, good crystallinity and high conductivity, and can prepare high-purity lithium phosphide powder in a large scale at low cost.
Description
Technical Field
The present invention relates to Li 3 The technical field of P crystal, in particular to Li 3 Preparation method of P crystal powder and Li prepared by method 3 P crystal powder and its application.
Background
Li 3 The P crystal is a semiconductor material and has good application prospect in the field of semiconductors. The special layered structure, high specific capacity and proper potential range of the lithium ion battery lead the lithium ion battery to have potential application prospect in the aspects of lithium battery cathode materials, solid electrolytes and lithium supplement agents. However, the preparation methods of lithium phosphide are few, mainly ball milling and high-temperature calcination.
Both patent CN104627972 and patent CN113097477A use ball milling method.
Patent CN104627972 discloses a preparation method of lithium phosphide powder: lithium phosphide powder is prepared by ball milling lithium hydride and phosphorus powder. However, lithium hydride can have violent chemical reaction when meeting water to generate flammable and explosive hydrogen, so that potential safety hazards exist in the manufacturing process, and the reaction time is long. In addition, the crystallinity of the prepared lithium phosphide powder is poor as can be seen from the provided XRD pattern.
The patent CN113097477 discloses a preparation method of lithium phosphide powder: mixing molten metal lithium and phosphorus powder, grinding the mixture with the lithium powder in an inert environment, and preparing the lithium phosphide material by a method of firstly carrying out solid phase and then carrying out ball milling. The method also has the defects of long preparation period and easy introduction of impurities. Notably, in this patent, no data are provided for the crystallinity, purity, or performance characterization of the product, or even whether it successfully produced the target product.
Patent CN111039269 discloses a method for preparing lithium phosphide powder by adopting a high-temperature calcination method, which directly compounds and generates metal lithium and red phosphorus powder by high-temperature calcination in an inert environment. However, the method requires a long time of calcination at high temperature, and the energy consumption is large. Because the metal lithium with higher activity is adopted for calcination, higher potential safety hazard also exists.
In addition, a preparation method of a lithium phosphide composite material is reported in a patent, for example, patent CN114094055 discloses a preparation method of a lithium phosphide electrode, which comprises the steps of mixing lithium phosphate with phenolic resin, adding alcohol as a solvent, uniformly mixing the materials by a shearing emulsification method, heating at a low temperature to remove the alcohol and curing to obtain a material with nano lithium phosphide particles coated by a carbon shell, wherein the lithium phosphide prepared by the method contains impurities such as carbon.
In conclusion, the existing preparation method of lithium phosphide has the defects of low purity and low crystallinity, or has the defects of high energy consumption and unsafe preparation process of lithium phosphide.
Li 3 The immaturity of the preparation method of P crystals directly leads to the immaturity of the research on the application thereof, currently in relation to Li 3 P crystal application studies are also very rare.
Li 3 The P crystal is used as a lithium supplementing agent of the anode of the solid lithium ion battery. Solid-state lithium ion batteries are receiving attention as promising future electric vehicle batteries due to their excellent safety and expectation of high energy density. Although the capacity of the negative electrode material (silicon, tin, phosphorus and the like) serving as the hot door of the solid-state lithium battery is high, a solid electrolyte interface is continuously formed on the surface of the negative electrode in the first charging process, so that the problems of poor cycle stability and low first coulombic efficiency of the negative electrode are caused, and the problem is one of the key problems that the solid-state lithium battery cannot be industrially applied. Although a great deal of experience is also accumulated when the liquid lithium ion battery is used for solving the problem, the problem can be effectively solved by adopting the positive electrode lithium supplement with simple operation and low cost, but the experience cannot be directly transplanted into the solid lithium battery. The common positive electrode lithium-supplementing agent can be divided into Li 2 C 2 O 4 Organic lithium-containing compounds represented by and Li 2 O、Li 2 O 2 、Li 2 S、Li 3 Inorganic lithium-containing compounds represented by N. Wherein, Li 2 C 2 O 4 、Li 2 O、Li 2 O 2 And Li 3 N and the like can release gas in the lithium supplement decomposition reaction, so that the electrode structure is greatly damaged, and the cycle life of the battery is shortened; li has also been reported 2 S is taken as a positive electrode lithium supplement agent, but the lithiation voltage of sulfur mainly occurs at about 2.3V and is overlapped with the working voltage range of the positive electrode, and Li 2 The S/S can participate in the charge and discharge circulation of the battery, and the working voltage is not ideal. Moreover, the lithium-supplementing agents are electronic insulators, and a high proportion (more than 30 wt%) of carbon or metal is required to be added to improve the electronic conductivity of the lithium-supplementing agents when the lithium-supplementing agents are used, so that the practical available capacity of the lithium-supplementing agents is sacrificed, and the solid electrolyte is strongly decomposed due to the addition of a large amount of the conductive agents such as carbon, and the performance of the battery is greatly influenced. Furthermore, with the exception of Li 3 Besides N, the lithium ion conductivity of these lithium supplements is also generally low, and can only be applied to liquid lithium ion batteries, mainly because the ion channels in the electrodes of the liquid lithium ion batteries are mainly provided by the electrolyte permeating into the electrodes. In a solid-state lithium ion battery, lithium ions are conducted at a solid-solid interface, and therefore, a lithium supplement agent is required to have good lithium ion conductivity. Therefore, the existing positive electrode lithium supplement agents do not meet the strict requirements of the solid-state lithium ion battery. Li 3 The P crystal has 1547.61mAh g -1 The decomposition potential is 1V, which is far lower than the cut-off voltage of the anode. Delithiation of lithium phosphide in positive electrode is an irreversible process, which only participates in the first charging process, and Li 3 The P crystal has high lithium ion conductivity and electronic conductivity, can be used as a positive electrode lithium supplement agent to be directly mixed with a positive electrode material, and is an ideal positive electrode lithium supplement material of a solid-state lithium ion battery. Thus, high purity Li is prepared 3 The P crystal is used as a positive electrode lithium supplement agent of the all-solid-state lithium battery, a good lithium supplement scheme of the solid-state lithium ion battery is provided, and the technical problem which is expected to be solved but is not successful all the time can be solved.
Disclosure of Invention
In view of this, the present invention provides a Li 3 The preparation method of the P crystal powder comprises the following steps:
s1, removing oxide on the surfaces of red phosphorus and lithium to obtain pretreated red phosphorus and pretreated lithium, and storing in inert gas for later use;
s2, dissolving the polycyclic aromatic hydrocarbon into an organic solvent to prepare polycyclic aromatic hydrocarbon organic solution;
s3, dissolving the pretreated lithium prepared in the step S1 into the polycyclic aromatic hydrocarbon organic solution prepared in the step S2 to prepare a lithiated solution;
s4, adding the pretreated red phosphorus prepared in the step S1 into the lithiation solution prepared in the step S3, and fully stirring to obtain a mixture;
s5, centrifugally separating solid powder from the mixture prepared in the step S4, washing and drying to obtain powder;
s6, roasting and crushing the powder prepared in the step S5 to obtain Li 3 P crystal powder;
the steps S3 to S6 are all performed under an inert gas atmosphere, and the inert gas is one of argon and helium.
In some embodiments, the polycyclic aromatic hydrocarbon is one or more of biphenyl, dimethylbiphenyl, 3 '-dimethylbiphenyl, 4' -dimethylbiphenyl, p-terphenyl, naphthalene, anthracene, and the like; biphenyl, naphthalene and anthracene are preferred.
In some embodiments, the organic solvent is one or more of diethyl ether, dimethyl ether, methyl butyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, tetrahydropyran, dimethyl tetrahydrofuran, ethyl methyl carbonate, ethylene carbonate, propylene carbonate, and dimethyl carbonate. Diethylene glycol dimethyl ether and tetrahydrofuran are preferred.
In some embodiments, the concentration of the polycyclic aromatic hydrocarbon in the organic solution of polycyclic aromatic hydrocarbon in the step S2 is 0.05mol/L to 5 mol/L.
In some embodiments, the method for preparing the lithiation solution in step S3 includes the following steps: under the protection of inert gas atmosphere, adding the metal lithium pretreated in the step S1 into the organic solution of the polycyclic aromatic hydrocarbon compound, and stirring until the metal lithium is completely dissolved, wherein the mass ratio of the metal lithium to the polycyclic aromatic hydrocarbon is 1: 1.
in some embodiments, the mass ratio of the metallic lithium added in the step S3 to the red phosphorus added in the step S4 is (3.1-9): 1.
In some embodiments, the firing conditions of step S6 are low temperature firing: in the atmosphere of inert gas protection, the roasting temperature is 200-600 ℃, and the roasting time is 1-4 h.
It is a second object of the present invention to provide Li prepared by the above method 3 P crystal powder.
The third object of the present invention is Li 3 The P crystal powder is used as a lithium supplement agent of a solid lithium ion battery.
In some embodiments, the Li 3 Sigma of P crystal powder e Up to 1.07x 10 -3 S cm -1 ，σ i Up to 1.94x 10 - 3 S cm -1 To achieve 10 -3 S cm -1 A rank.
Compared with the prior art, the invention has the beneficial effects that:
1、Li 3 the P crystals are not prepared by direct calcination of metallic lithium but by less active, low crystallinity Li 3 P is calcined, so that the safety of the preparation process is greatly improved.
2. The production period is short, the energy consumption is low, the quality of products prepared in different batches is stable, the batch preparation can be realized, and the industrial production is facilitated.
3. The product has high purity and good crystallinity, simultaneously has high lithium ion conductivity and electronic conductivity, can be directly mixed with a positive electrode material of a solid-state lithium ion battery to be used as a positive electrode lithium supplement agent, solves the problems of poor cycle stability of a negative electrode and low first coulombic efficiency, and promotes the development process of industrial application of the solid-state lithium ion battery.
Drawings
FIG. 1 Li of the invention 3 A preparation flow chart of the P crystal.
Figure 2 comparison of XRD patterns of the products of examples 1-3.
Figure 3 XRD spectrum comparison of comparative example 1 product.
Figure 4 comparison of XRD patterns of the product of comparative example 2.
FIG. 5 Li measured under different ion-blocking, electron-blocking electrodes 3 P crystal AC impedance test chart, wherein, a is Li 6 PS 5 Cl is an electron blocking electrode; b, using a stainless steel sheet as an ion blocking electrode; c, using a stainless steel sheet as an ion blocking electrode.
FIG. 6 different Li 3 First-loop charge-discharge curve of full cell with P crystal content.
FIG. 7 different Li 3 Full cell cycle capacity curve for P crystal content.
Detailed Description
The principles and features of this invention are described below in conjunction with examples which are set forth to illustrate, but are not to be construed to limit the scope of the invention.
Preparation of Li in accordance with the invention 3 Under the protection of inert gas, the P crystal is prepared through the reaction of metal lithium and polycyclic aromatic hydrocarbon at normal temperature to form polycyclic aromatic hydrocarbon lithium, the reaction with red phosphorus to prepare low-crystallinity lithium phosphide, and the low-temperature roasting to raise the crystallinity to obtain high-crystallinity Li 3 P crystal. The preparation flow chart is shown in figure 1.
In the reaction raw material, the metal lithium may be a lithium sheet, a lithium strip, a lithium particle, a lithium foil, or the like, and the shape thereof is not limited. The surface oxide is removed by grinding.
The method for removing the oxide on the surface of the red phosphorus comprises the following steps: boiling red phosphorus in boiling water for 30min, filtering, washing, and drying to obtain pretreated red phosphorus; the drying conditions were: vacuum drying at 35 deg.C for 2 h.
The polycyclic aromatic hydrocarbon in the invention is used for preparing the lithiation solution by reacting with metal lithium, as long as the polycyclic aromatic hydrocarbon can react with lithium to generate the polycyclic aromatic hydrocarbon lithium, and the polycyclic aromatic hydrocarbon can be one or more of biphenyl, dimethyl biphenyl, 3 '-dimethyl biphenyl, 4' -dimethyl biphenyl, p-terphenyl, naphthalene and anthracene, but is not limited to the polycyclic aromatic hydrocarbon compound. Because the reaction of the polycyclic aromatic hydrocarbon and the metallic lithium is exothermic, an organic solvent is added for dilution. The organic solvent is used for dissolving the polycyclic aromatic hydrocarbon and the polycyclic aromatic hydrocarbon lithium, and can be one or more of diethyl ether, dimethyl ether, methyl butyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, tetrahydropyran, dimethyl tetrahydrofuran, methyl ethyl carbonate, ethylene carbonate, propylene carbonate and dimethyl carbonate, but is not limited to the organic solvent. Ethylene glycol dimethyl ether and tetrahydrofuran are preferred.
Preferably, the polycyclic aromatic hydrocarbon is diluted in an organic solvent and then reacted with lithium metal. The concentration of the polycyclic aromatic hydrocarbon organic solution is preferably 0.05mol/L to 5 mol/L. The concentration is too low, the concentration of the prepared product is too low, and the preparation efficiency is low. Too high concentration, too violent reaction and difficult control.
The amount of lithium added is determined by the amount of polycyclic aromatic hydrocarbon in the polycyclic aromatic hydrocarbon organic solution, and the mass ratio of the two is 1: 1.
Lithium metal is made into lithium solution of polycyclic aromatic hydrocarbon lithium and then reacts with red phosphorus to prepare lithium phosphide with low crystallinity. In this reaction, the amount of lithium polycyclic aromatic hydrocarbon should be excessive in order to increase the degree of red phosphorus reaction. Specifically, the quantity ratio of the added quantity of the lithium metal reacted with the polycyclic aromatic hydrocarbon to the added quantity of the red phosphorus is (3.1-9): 1.
The polycyclic aromatic hydrocarbon lithium and red phosphorus are reduced into polycyclic aromatic hydrocarbon, and the polycyclic aromatic hydrocarbon can be repeatedly used after being processed, so that the preparation method has the advantages of environmental protection and low cost.
The inventor finds that the crystallinity of lithium phosphide has a great influence on the conductivity in the research process. When the low crystallinity is low, lithium phosphide is poor in conductivity and cannot be used as a positive electrode lithium-supplementing agent for a solid-state lithium ion battery. After the crystallinity of the lithium phosphide crystal is improved by roasting, the electronic conductivity of the lithium phosphide crystal is obviously improved, so that the prepared lithium phosphide crystal has high electronic conductivity and ionic conductivity.
The roasting process adopts low-temperature roasting, and the roasting time is 1-4 h at 200-600 ℃. The temperature is lower than 200 ℃, the crystallinity is not high, and the lithium ion battery can not be used as a positive pole lithium supplement agent of a solid lithium ion battery. Li with high crystallinity can be obtained even in the range of 600 ℃ to 1200 DEG C 3 P crystal, but high energy consumption, and therefore, 200 ℃ to 600 ℃ is preferable.
The inert gas in the preparation process is one of argon and helium, and aims to protect raw materials, intermediate products and products from reacting with air.
The present invention will be described with reference to specific examples, in which the reagents used are all commercially available reagents. The purity of red phosphorus is more than 90 percent, and the purity of lithium is more than 99 percent.
Example 1
This example provides a method for preparing Li 3 The method for preparing the P crystal powder comprises the following steps:
s1, adding 150mL of deionized water into a 250mL beaker, adding 100g of red phosphorus after boiling, heating and boiling for 30 minutes, washing the precipitate with hot water, performing suction filtration, then placing the precipitate into a vacuum drying oven, drying the precipitate at 35 ℃ for 2 hours, grinding the precipitate, vacuumizing the precipitate, and then placing the ground precipitate into a glove box filled with argon for later use. And after polishing the lithium sheet to remove surface oxides, putting the lithium sheet into a glove box filled with argon for later use.
S2, in a glove box, 3.70g (24.0mmol) of biphenyl was added into a glass bottle containing 12mL of tetrahydrofuran, and after complete dissolution, a biphenyl tetrahydrofuran solution with a concentration of 2mol/L was obtained.
S3, adding 167mg (24.0mmol) of polished lithium sheets into the biphenyl tetrahydrofuran solution in the glove box, sealing, standing for 4 hours, and preparing the biphenyl lithium lithiation solution after the metal lithium is dissolved until the solution becomes bluish black.
S4, adding 82.80mg (2.67mmol) of treated red phosphorus into the lithium biphenyl lithium solution, placing the solution on a magnetic stirrer at room temperature, stirring for 6 hours, pouring the solution into a centrifuge tube, sealing the centrifuge tube, taking the solution out of a glove box, centrifuging, washing solid substances obtained by centrifuging in the glove box by tetrahydrofuran until the solid substances are clear, placing the solid substances in a transition bin of the glove box, vacuumizing and drying at room temperature for 30 minutes, and drying to obtain powder.
S5, sealing the powder in a container filled with argon, placing the container into a muffle furnace for roasting, raising the temperature to 600 ℃ at the rate of 5 ℃/min, and preserving the heat for 1 h.
S6, naturally cooling to room temperature after roasting, taking out the product in a glove box, and grinding to obtain Li 3 P crystal powder.
Example 2
The embodiment is providedFor one kind of preparation of Li 3 The method for preparing the P crystal powder comprises the following steps:
s1 same as example 1
S2, 0.96g (7.5mmol) of naphthalene is added into a glass bottle filled with 150mL of ethylene glycol dimethyl ether filled with argon gas, and after complete dissolution, a naphthalene glycol dimethyl ether solution is prepared.
S3, adding 52.06mg (7.5mmol) of polished lithium foil into the naphthalene glycol dimethyl ether solution, sealing, standing for 3 hours until the lithium metal is dissolved until the solution becomes blue-black, and preparing the lithium naphthalene solution with the concentration of 0.05 mol/L.
S4, adding 46.45mg (1.5mmol) of treated red phosphorus into the lithium naphthalene lithiation solution, placing the solution on a magnetic stirrer at room temperature, stirring for 6 hours, pouring the solution into a centrifuge tube, sealing the centrifuge tube, taking the solution out of a glove box, centrifuging, washing solid substances obtained by centrifuging in the glove box by using ethylene glycol dimethyl ether until the solid substances are clear, placing the solid substances in a transition bin of the glove box, vacuumizing and drying at room temperature for 30 minutes, and drying to obtain powder.
S5, sealing the powder in a container filled with argon, placing the container into a muffle furnace for roasting, raising the temperature to 200 ℃ at a rate of 5 ℃/min, and preserving the heat for 4 hours.
S6, naturally cooling to room temperature after roasting, taking out the product in a glove box, and grinding to obtain Li 3 P crystal powder.
Example 3
This example provides a method for preparing Li 3 The method for preparing the P crystal powder comprises the following steps:
s1 same as example 1
S2, in a glove box, 13.67g (75mmol) of 4,4 '-dimethylbiphenyl was added into a glass bottle containing 15mL of ethylene glycol dimethyl ether, and after complete dissolution, a 5 mol/L4, 4' -dimethylbiphenyl ethylene glycol dimethyl ether solution was prepared.
S3, adding 520.57mg (75mmol) of polished lithium sheets into the 4,4 '-dimethyl diphenyl ethylene glycol dimethyl ether solution in the glove box, sealing, standing for 10 hours until the lithium metal is dissolved until the solution becomes bluish black, and preparing the 4, 4' -dimethyl diphenyl lithium lithiation solution.
S4, adding 749.27mg (24.2mmol) of treated red phosphorus into the 4, 4' -dimethyl diphenyl lithium lithiation solution, placing the solution on a magnetic stirrer at room temperature, stirring for 6 hours, pouring the solution into a centrifuge tube, sealing the centrifuge tube, taking the solution out of a glove box, centrifuging, washing solid substances obtained by centrifuging in the glove box by using ethylene glycol dimethyl ether until the solid substances are clear, placing the solid substances in a transition bin of the glove box, vacuumizing and drying at room temperature for 30 minutes, and drying to obtain powder.
S5, sealing the powder in a container filled with argon, placing the container into a muffle furnace for roasting, raising the temperature to 400 ℃ at the rate of 5 ℃/min, and preserving the heat for 2 h.
S6, naturally cooling to room temperature after roasting, taking out the product in a glove box, and grinding to obtain Li 3 P crystal powder.
Comparative example 1
Comparative example 1 the same as example 1, but without baking in S5, the powder of step S4 was directly ground.
Comparative example 2
Comparative example 2 the same as example 1, but during the calcination, the container holding the powder was not protected by argon.
Experimental example 1
XRD tests were carried out on the products of examples 1-3 and comparative examples 1-2 under the following conditions: the products prepared in examples 1-3 were mixed well and sampled for testing. The products prepared in comparative example 1 and comparative example 2 were sampled separately for testing. The diffraction angle 2 θ of the samples prepared in examples 1 to 3 and comparative example 1 was 10 ° -80 ° . The sample prepared in comparative example 2 was tested for diffraction angle 2 θ of 10 ° -70 ° 。
Experimental example 2
Test and analysis method for Li by electrochemical impedance spectroscopy experiment 3 The P crystal was resistance tested using an iviumstat model a88417 from the Ivium manufacturer. The specific test method comprises the following steps: the samples prepared in examples 1 to 3 were mixed uniformly in a glove box, and 100mg of the mixture was taken, pressed into 0.90mm thin sheets by a solid state die and subjected to pressure holding, each with Li 6 PS 5 Cl (25mg) as an electron blocking electrode and stainless steel as an ion blocking electrode, Li was tested 3 Ionic resistance of P crystal. Test Li with stainless steel sheet as ion blocking electrode sheet 3 Electron resistance of P crystal, thereby calculating Li 3 Ionic conductivity and electronic conductivity of P.
The ionic conductivity and the electronic conductivity of the sample prepared in comparative example 1 were measured in the same manner.
Experimental example 3
After the samples prepared in examples 1 to 3 were mixed uniformly, all-solid batteries were sampled to test their lithium-supplementing properties. The manufacturing method and the testing method of the all-solid-state battery comprise the following steps: in lithium cobaltate (LiCoO) 2 ) Li with different contents is added into the anode material 3 P crystal powder, sulfide electrolyte Li 6 PS 5 Cl is used as a solid electrolyte, and is assembled with a graphite cathode to form an all-solid-state battery, and the performance of the all-solid-state battery is tested by charging and discharging at 0.1C. In the charge and discharge test system, the test voltage range is 2.5-4.2V. Three kinds of Li are prepared 3 All-solid-state batteries with P crystal powder added amount are respectively Li 3 The addition amount of the P crystal powder is 0%, 2% and 5% of the weight of the positive electrode material.
From FIGS. 2 to 4, which are XRD patterns of the samples of examples 1 to 3, comparative examples 1 and 2, respectively, and a standard pattern below the XRD patterns, it can be seen that the products prepared in examples 1 to 3 are indeed Li 3 The P crystal has high purity and high crystallinity. The product of comparative example 1, however, had a lower crystallinity without calcination. Comparative example 2 in the preparation process, calcination was not carried out in an inert gas, and the product was not pure, and Li was produced 3 PO 4 。
FIG. 5 is a graph showing the AC impedance measurements of samples prepared in examples 1-3 under different ion-blocking, electron-conducting electrode materials and electron-blocking, ion-conducting electrode materials, wherein a is Li 6 PS 5 Cl is an electron blocking electrode; b, using a stainless steel sheet as an ion blocking electrode; c, using a stainless steel sheet as an ion blocking electrode. FIG. 5a is Li 6 PS 5 Cl (25mg) as an electron blocking electrode, the semicircle of the high frequency region representing Li 3 P and Li 6 PS 5 Cl phase conductivity, i.e. resulting in a total ionic transport resistance R 1 96 Ω. FIG. 5b is an AC impedance test using a stainless steel sheet as an ion blocking electrode, and a semicircle in the high frequency region represents Li 6 PS 5 Bulk phase conduction of Cl and ion transport resistance of R 2 Not higher than 37 Ω, therefore, Li 3 P has an ionic resistance of R i 96-37 ═ 59 Ω, where 100mg of Li 3 P thickness of 0.90mm, calculated to give Li 3 Ion conductivity of P is σ i ＝1.94x 10 -3 S cm -1 . FIG. 5c shows the point where the semicircle intersects the solid axis at low frequency, corresponding to the electronic resistance R, using stainless steel as the ion blocking electrode e ，R e 107 Ω, with 100mg of Li 3 P is 0.90mm thick, and sigma is obtained by calculation e ＝1.07x 10 -3 S cm -1 . Therefore, the Li prepared by the invention is measured by an electrochemical impedance spectroscopy experimental test and analysis method 3 P has higher electron conductivity and ion conductivity which can reach 10 -3 S cm -1 A rank.
The sample of comparative example 1 was also tested for electronic conductivity and ionic conductivity in the same manner, but the electronic conductivity and ionic conductivity were too small, the impedance was too large, and the test range of the instrument was exceeded, and no valid data could be obtained. And can not be directly used as a lithium supplement agent of a solid lithium ion battery.
FIG. 6 shows different Li 3 First-loop charge-discharge curve of full cell with P crystal content. With Li 3 Increase in P Crystal content due to decomposed Li 3 The contribution of the P crystal to the battery capacity, the charge and discharge capacity are increased. When 5% of Li is added 3 When P crystal is formed, the first-circle discharge capacity is 132mAh g -1 The theoretical capacity of lithium cobaltate has been reached. FIG. 6 shows different Li 3 Full cell cycle capacity curve for P crystal content. As can be seen from FIG. 7, the discharge capacity of the battery (0%) to which no lithium phosphide was added was only 60.3mAh g after 100 cycles -1 The capacity retention rate is 56 percent, and the discharge capacity of the 5 percent lithium phosphide battery is added to be 106.6mAh g -1 The capacity retention rate was 80%. Further validation of our synthesized Li 3 P crystalThe lithium ion battery has high ionic conductivity and electronic conductivity, has good positive electrode pre-lithiation capacity in a solid lithium ion battery, and can solve the problems of poor negative electrode cycling stability and low first coulombic efficiency.
The above embodiments are only for illustrating the technical idea and features of the present invention, and the purpose of the present invention is to enable those skilled in the art to understand the content of the present invention and implement the present invention, and not to limit the protection scope of the present invention by this means. All equivalent changes and modifications made according to the spirit of the present invention should be covered in the protection scope of the present invention.
Claims (10)
1. Li 3 The preparation method of the P crystal powder is characterized by comprising the following steps:
s1, removing oxide on the surfaces of red phosphorus and lithium to obtain pretreated red phosphorus and pretreated lithium, and storing in inert gas for later use;
s2, dissolving the polycyclic aromatic hydrocarbon into an organic solvent to prepare polycyclic aromatic hydrocarbon organic solution;
s3, dissolving the pretreated lithium prepared in the step S1 into the polycyclic aromatic hydrocarbon organic solution prepared in the step S2 to prepare a lithiated solution;
s4, adding the pretreated red phosphorus prepared in the step S1 into the lithiation solution prepared in the step S3, and fully stirring to obtain a mixture;
s5, centrifugally separating solid powder from the mixture prepared in the step S4, washing and drying the solid powder to obtain powder;
s6, roasting and crushing the powder prepared in the step S5 to obtain Li 3 P crystal powder;
the steps S3 to S6 are all performed under an inert gas atmosphere.
2. Li according to claim 1 3 The preparation method of the P crystal powder is characterized by comprising the following steps: the polycyclic aromatic hydrocarbon is one or more of biphenyl, dimethyl biphenyl, 3 '-dimethyl biphenyl, 4' -dimethyl biphenyl, p-terphenyl, naphthalene, anthracene and the like; the organic solvent is diethyl ether, dimethyl ether, methyl butyl ether, ethylene glycol dimethyl ether, diethyl etherOne or more of glycol dimethyl ether, tetrahydrofuran, tetrahydropyran, dimethyl tetrahydrofuran, methyl ethyl carbonate, ethylene carbonate, propylene carbonate and dimethyl carbonate.
3. Li according to claim 1 3 The preparation method of the P crystal powder is characterized by comprising the following steps: the concentration of the polycyclic aromatic hydrocarbon in the polycyclic aromatic hydrocarbon organic solution in the step S2 is 0.05mol/L-5 mol/L.
4. Li according to claim 3 3 The preparation method of the P crystal powder is characterized by comprising the following steps: the preparation method of the lithiation solution in the step S3 comprises the following steps: dissolving all the metallic lithium pretreated in the step S1 into the organic solution of the polycyclic aromatic hydrocarbon compound, wherein the mass ratio of the metallic lithium to the polycyclic aromatic hydrocarbon is 1: 1.
5. li according to claim 4 3 The preparation method of the P crystal powder is characterized by comprising the following steps: the mass ratio of the metal lithium added in the step S3 to the red phosphorus added in the step S4 is (3.1-9): 1.
6. Li according to claim 1 3 The preparation method of the P crystal powder is characterized by comprising the following steps: the inert gas is one of argon and helium.
7. Li according to any one of claims 1 to 6 3 The preparation method of the P crystal powder is characterized by comprising the following steps: the roasting conditions are as follows: the roasting temperature is 200-600 ℃, and the roasting time is 1-4 h.
8. Li according to any one of claims 1 to 7 3 P crystal powder.
9. Li according to claim 8 3 The P crystal powder is used as a lithium supplement agent for the anode of the solid lithium ion battery.
10. As in claimClaim 9 of Li 3 The application of the P crystal powder as the lithium supplement agent of the anode of the solid lithium ion battery is characterized in that: the Li 3 Sigma of P crystal powder e ≥10 -3 S cm -1 ，σ i ≥10 -3 S cm -1 。
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