CN110424048A - A kind of non-linear optical crystal material and preparation method and application - Google Patents

A kind of non-linear optical crystal material and preparation method and application Download PDF

Info

Publication number
CN110424048A
CN110424048A CN201910688550.XA CN201910688550A CN110424048A CN 110424048 A CN110424048 A CN 110424048A CN 201910688550 A CN201910688550 A CN 201910688550A CN 110424048 A CN110424048 A CN 110424048A
Authority
CN
China
Prior art keywords
optical crystal
crystal material
linear optical
preparation
surfactant
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201910688550.XA
Other languages
Chinese (zh)
Inventor
李志华
曹国炜
郄元元
罗楠楠
张敏
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shandong Normal University
Original Assignee
Shandong Normal University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shandong Normal University filed Critical Shandong Normal University
Priority to CN201910688550.XA priority Critical patent/CN110424048A/en
Publication of CN110424048A publication Critical patent/CN110424048A/en
Pending legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C30CRYSTAL GROWTH
    • C30BSINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/10Inorganic compounds or compositions
    • C30B29/12Halides
    • CCHEMISTRY; METALLURGY
    • C30CRYSTAL GROWTH
    • C30BSINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B7/00Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions
    • C30B7/10Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions by application of pressure, e.g. hydrothermal processes
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/052Li-accumulators
    • H01M10/0525Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/362Composites
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/48Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/483Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Composite Materials (AREA)
  • Manufacturing & Machinery (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

Present disclose provides a kind of non-linear optical crystal material and preparation method and applications, preparation method are as follows: NBBF is prepared using low-temperature hydrothermal synthetic method, surfactant is added in low-temperature hydrothermal synthetic system, the ratio of the concentration in the reaction time and surfactant of low-temperature hydrothermal synthesis is not less than 12:0.01, h:molL‑1.Disclosure preparation process is easy to operate, at low cost, reproducible, and yield is high, and there is universality and large-scale production to be worth.The non-linear optical crystal material that the disclosure provides has more excellent electrochemistry cycle performance.

Description

A kind of non-linear optical crystal material and preparation method and application
Technical field
The disclosure belongs to non-linear optical crystal material preparation technical field, be related to a kind of non-linear optical crystal material and Preparation method and application.
Background technique
Here statement only provides background information related with the disclosure, without necessarily constituting the prior art.
The electrode material of lithium ion battery is mostly layer structure, is conducive to Li+It is freely embeddable and deviates from, still, with following For ring using the extension of time or under inappropriate use state, battery often will appear bulging even explosion phenomenon, Ren Mentong Cross the stability that some technological means such as coating technology etc. improves battery material.The structure list of non-linear optical crystal material NBBF Member [Be2BO3F2] by [a BO3] and two [BeO3F] composition, and there are two types of the six of form in each basic structural unit Member ring.The dihedral angle degree of two interplanars is 14.32 °, by sharing oxygen atom, [Be2BO3F2] ring formed along (100) direction Unlimited stratiform, the ligancy of oxygen atom are 3, and adjacent is combined between layers with electrostatic force, and spacing between layers It is larger, there is apparent layer growth habit, the interlamellar spacing of the crystalline material is sufficiently large, is easy to Li+Pass through, and their single layer Six-membered ring structure is highly stable, can become a kind of novel electrode material.What use was more at present is high-temperature solid-phase sintering method, Reaction condition requires very high, complex process.
Summary of the invention
The disclosed invention artificially solves the problems, such as that reaction condition existing for high-temperature solid-phase sintering method preparation NBBF is demanding, grinds Numerous preparation methods is studied carefully, has been found in numerous methods, can have been prepared using low temperature (being lower than 300 DEG C) hydrothermal synthesis method NBBF.However, influence of the temperature to pattern is very big it is discovered by experiment that low-temperature hydrothermal synthetic method is prepared in the condition of NBBF, temperature The accuracy controlling of degree generally requires more accurate system equipment and is regulated and controled, higher cost, and the decline of temperature performance of control It will lead to the poor reproducibility for preparing band-like NBBF.
In order to solve the deficiencies in the prior art, purpose of this disclosure is to provide a kind of non-linear optical crystal material and preparations Method and application, can effectively solve the problem that influence of the temperature to NBBF pattern.
To achieve the goals above, the technical solution of the disclosure are as follows:
The disclosure in a first aspect, a kind of preparation method of non-linear optical crystal material is provided, using low-temperature hydrothermal Synthetic method prepares NBBF, and surfactant, the reaction time of low-temperature hydrothermal synthesis and table are added in low-temperature hydrothermal synthetic system The ratio of the concentration of face activating agent is not less than 12:0.01, h:molL-1
The disclosure is found through experiments that: firstly, the self assembly effect using surfactant can form glue in the solution The self-assemblies such as group, liquid crystal, vesica can effectively control the pattern of NBBF;Secondly, surfactant concentration is bigger, it is required anti- Longer between seasonable, if surfactant concentration is larger, and the reaction time is shorter, then can not obtain band-like NBBF, or even can not obtain Obtain NBBF.
Another aspect of the present disclosure provides a kind of the non-thread of the preparation method acquisition of above-mentioned non-linear optical crystal material Property optical crystal material.
The third aspect of the disclosure provides a kind of above-mentioned non-linear optical crystal material answering in electrochemical field With.
Show that it after circulation 20 times, is filled using the characterization experiment that the NBBF of disclosure preparation carries out efficiency for charge-discharge Discharging efficiency reaches 98.9%.Compared with the non-linear optical crystal material for not using surfactant preparation, disclosure preparation NBBF have more excellent electrochemistry cycle performance.
The fourth aspect of the disclosure provides a kind of electrode material, including above-mentioned non-linear optical crystal material.
The disclosure has the beneficial effect that
(1) disclosure preparation process is easy to operate, at low cost, reproducible, and yield is high, has universality and large-scale production Value.
(2) disclosure prepares non-linear optical crystal material with biggish interlamellar spacing and layer growth habit, in conjunction with it Structure feature;The non-linear optical crystal material that the disclosure provides simultaneously has more excellent electrochemistry cycle performance.
Detailed description of the invention
The Figure of description for constituting a part of this disclosure is used to provide further understanding of the disclosure, and the disclosure is shown Meaning property embodiment and its explanation do not constitute the improper restriction to the disclosure for explaining the disclosure.
Fig. 1 is the X-ray diffraction spectrogram of NBBF non-linear optical crystal material prepared by the embodiment of the present disclosure 1;
Fig. 2 is the transmission electron microscope photo of NBBF non-linear optical crystal material prepared by the embodiment of the present disclosure 1, ratio in figure Ruler is 1 μm;
Fig. 3 is the transmission electron microscope photo of NBBF non-linear optical crystal material prepared by the embodiment of the present disclosure 2, ratio in figure Ruler is 1 μm;
Fig. 4 is the transmission electron microscope photo of NBBF non-linear optical crystal material prepared by the embodiment of the present disclosure 3, ratio in figure Ruler is 1 μm;
Fig. 5 is the transmission electron microscope photo of NBBF non-linear optical crystal material prepared by the embodiment of the present disclosure 4, ratio in figure Ruler is 0.5 μm;
Fig. 6 is the transmission electron microscope photo of NBBF non-linear optical crystal material prepared by the embodiment of the present disclosure 5, ratio in figure Ruler is 1 μm;
Fig. 7 is the transmission electron microscope photo of NBBF non-linear optical crystal material prepared by the embodiment of the present disclosure 6, ratio in figure Ruler is 1 μm;
Fig. 8 is the transmission electron microscope photo of NBBF non-linear optical crystal material prepared by the embodiment of the present disclosure 7, ratio in figure Ruler is 1 μm;
Fig. 9 is the transmission electron microscope photo of NBBF non-linear optical crystal material prepared by the embodiment of the present disclosure 8, ratio in figure Ruler is 1 μm;
Figure 10 is the transmission electron microscope photo of NBBF non-linear optical crystal material prepared by the embodiment of the present disclosure 9, is compared in figure Example ruler is 1 μm;
Figure 11 is that the embodiment of the present disclosure 10 uses the NBBF non-linear optical crystal material of the preparation of embodiment 1 as lithium ion The electrode material of battery is with 0.5C (1C=140mAh/g) rate charge-discharge loop test 20 times charging and discharging curves;
Figure 12 is that the embodiment of the present disclosure 10 uses the NBBF non-linear optical crystal material of the preparation of embodiment 1 as lithium ion The electrode material of battery is with the relation curve of the efficiency for charge-discharge of 0.5C (1C=140mAh/g) rate charge-discharge and cycle-index.
Specific embodiment
It is noted that described further below be all exemplary, it is intended to provide further instruction to the disclosure.Unless another It indicates, all technical and scientific terms used herein has usual with disclosure person of an ordinary skill in the technical field The identical meanings of understanding.
It should be noted that term used herein above is merely to describe specific embodiment, and be not intended to restricted root According to the illustrative embodiments of the disclosure.As used herein, unless the context clearly indicates otherwise, otherwise singular Also it is intended to include plural form, additionally, it should be understood that, when in the present specification using term "comprising" and/or " packet Include " when, indicate existing characteristics, step, operation, device, component and/or their combination.
The problem of temperature during NBBF is affected to the pattern of pattern, the disclosure are prepared in view of low-temperature hydrothermal synthetic method Propose a kind of non-linear optical crystal material and preparation method and application.
A kind of exemplary embodiment of the disclosure provides a kind of preparation method of non-linear optical crystal material, uses Low-temperature hydrothermal synthetic method prepares NBBF, and surfactant, the reaction of low-temperature hydrothermal synthesis are added in low-temperature hydrothermal synthetic system The ratio of the concentration of time and surfactant is not less than 12:0.01, h:molL-1
The disclosure is found through experiments that: firstly, the self assembly effect using surfactant can form glue in the solution The self-assemblies such as group, liquid crystal, vesica can effectively control the pattern of NBBF;Secondly, surfactant concentration is bigger, it is required anti- Longer between seasonable, if surfactant concentration is larger, and the reaction time is shorter, then can not obtain band-like NBBF, or even can not obtain Obtain NBBF.
In one or more embodiments of the embodiment, step are as follows:
By H3BO3、BeSO4, NaF be added into surfactant solution, adjust pH be 11.5~12.5, under confined conditions, 200~220 DEG C are heated to be reacted.
In one or more embodiments of the embodiment, H3BO3、BeSO4, NaF molar ratio be 1:2.0~2.3:2.0 ~2.5.
In one or more embodiments of the embodiment, the concentration of surfactant is 0.02~0.06molL-1, instead It is 1~3 day between seasonable.
In one or more embodiments of the embodiment, the material after reaction removes supernatant liquor, and washing of precipitate is done Dry acquisition non-linear optical crystal material.
In one or more embodiments of the embodiment, the surfactant is lauryl sodium sulfate, poly- second two Alcohol or dodecyl trimethyl ammonium bromide
In the series embodiment, successively washed using second alcohol and water.
In the series embodiment, dry temperature is 80~90 DEG C, and drying time is 22~26h.
The another embodiment of the disclosure, the preparation method for providing a kind of above-mentioned non-linear optical crystal material obtain Non-linear optical crystal material.
Embodiment there is provided a kind of above-mentioned non-linear optical crystal materials in electrochemical field for the third of the disclosure Application.
Show that it after circulation 20 times, is filled using the characterization experiment that the NBBF of disclosure preparation carries out efficiency for charge-discharge Discharging efficiency reaches 98.9%.Compared with the non-linear optical crystal material for not using surfactant preparation, disclosure preparation NBBF have more excellent electrochemistry cycle performance.
Embodiment there is provided a kind of electrode materials, including above-mentioned non-linear optical crystal material for the 4th kind of the disclosure.
In order to enable those skilled in the art can clearly understand the technical solution of the disclosure, below with reference to tool The technical solution of the disclosure is described in detail in the embodiment of body.
Embodiment 1
(1) 20mL 0.02molL is configured-1Lauryl sodium sulfate be placed in the autoclave of 25mL, stir 5 points Clock.
(2) 0.09165g H is weighed3BO3、0.3418g BeSO4, 0.1492g NaF be added step (1) in reaction kettle In, it is stirred on magnetic stirring apparatus to being completely dissolved.
(3) in the solution whipping process of step (2), 1molL is constantly added dropwise-1NaOH solution adjusts pH value of solution 12, continue stirring 15 minutes, is uniformly mixed solution.
(4) autoclave of step (3) mixed solution is put into baking oven, is reacted for 24 hours in 200 DEG C of baking ovens.Instead It is cooled to room temperature after should stopping, arrest reaction kettle outwells supernatant, and the white for washing bottom with ethyl alcohol and deionized water is heavy It forms sediment, washs until neutrality, centrifugation obtains product.Product is dried in 85 DEG C of baking ovens for 24 hours to get nonlinear optical crystal material Expect NBBF.X-ray diffraction spectrogram is as shown in Figure 1, corresponding with the X-ray diffraction spectrogram in document.TEM Electronic Speculum such as Fig. 2 institute Show, is banded structure, meets target product.
Embodiment 2
(1) 20mL 0.02molL is configured-1Lauryl sodium sulfate be placed in the autoclave of 25mL, stir 5 points Clock.
(2) 0.09165g H is weighed3BO3、0.3418g BeSO4, 0.1492g NaF be added step (1) in reaction kettle In, it is stirred on magnetic stirring apparatus to being completely dissolved.
(3) in the solution whipping process of step (2), 1molL is constantly added dropwise-1NaOH solution adjusts pH value of solution 12, continue stirring 15 minutes, is uniformly mixed solution.
(4) autoclave of step (3) mixed solution is put into baking oven, reacts 3d in 200 DEG C of baking ovens.Reaction It being cooled to room temperature after stopping, arrest reaction kettle outwells supernatant, the white precipitate of bottom is washed with ethyl alcohol and deionized water, Until neutrality, centrifugation obtains product for washing.Product is dried in 85 DEG C of baking ovens for 24 hours to get non-linear optical crystal material NBBF.TEM Electronic Speculum meets target product as shown in figure 3, for banded structure.
Embodiment 3
(1) 20mL 0.02molL is configured-1Lauryl sodium sulfate be placed in the autoclave of 25mL, stir 5 points Clock.
(2) 0.09165g H is weighed3BO3、0.3418g BeSO4, 0.1492g NaF be added step (1) in reaction kettle In, it is stirred on magnetic stirring apparatus to being completely dissolved.
(3) in the solution whipping process of step (2), 1molL is constantly added dropwise-1NaOH solution adjusts pH value of solution 12, continue stirring 15 minutes, is uniformly mixed solution.
(4) autoclave of step (3) mixed solution is put into baking oven, is reacted for 24 hours in 220 DEG C of baking ovens.Instead It is cooled to room temperature after should stopping, arrest reaction kettle outwells supernatant, and the white for washing bottom with ethyl alcohol and deionized water is heavy It forms sediment, washs until neutrality, centrifugation obtains product.Product is dried in 85 DEG C of baking ovens for 24 hours to get nonlinear optical crystal material Expect NBBF.TEM Electronic Speculum meets target product as shown in figure 4, for banded structure.
Embodiment 4
(1) 20mL 0.06molL is configured-1Lauryl sodium sulfate be placed in the autoclave of 25mL, stir 5 points Clock.
(2) 0.09165g H is weighed3BO3、0.3418g BeSO4, 0.1492g NaF be added step (1) in reaction kettle In, it is stirred on magnetic stirring apparatus to being completely dissolved.
(3) in the solution whipping process of step (2), 1molL is constantly added dropwise-1NaOH solution adjusts pH value of solution 12, continue stirring 15 minutes, is uniformly mixed solution.
(4) autoclave of step (3) mixed solution is put into baking oven, is reacted for 24 hours in 200 DEG C of baking ovens.Instead It is cooled to room temperature after should stopping, arrest reaction kettle outwells supernatant, and the white for washing bottom with ethyl alcohol and deionized water is heavy It forms sediment, washs until neutrality, centrifugation obtains product.Product is dried in 85 DEG C of baking ovens for 24 hours to get nonlinear optical crystal material Expect NBBF.TEM Electronic Speculum cannot function as desired product as shown in figure 5, the forming of sample is bad.
Embodiment 5
(1) 20mL 0.06molL is configured-1Lauryl sodium sulfate be placed in the autoclave of 25mL, stir 5 points Clock.
(2) 0.09165g H is weighed3BO3、0.3418g BeSO4, 0.1492g NaF be added step (1) in reaction kettle In, it is stirred on magnetic stirring apparatus to being completely dissolved.
(3) in the solution whipping process of step (2), 1molL is constantly added dropwise-1NaOH solution adjusts pH value of solution 12, continue stirring 15 minutes, is uniformly mixed solution.
(4) autoclave of step (3) mixed solution is put into baking oven, reacts 3d in 200 DEG C of baking ovens.Reaction It being cooled to room temperature after stopping, arrest reaction kettle outwells supernatant, the white precipitate of bottom is washed with ethyl alcohol and deionized water, Until neutrality, centrifugation obtains product for washing.Product is dried in 85 DEG C of baking ovens for 24 hours to get non-linear optical crystal material NBBF.TEM Electronic Speculum meets target product as shown in fig. 6, for banded structure.
Embodiment 6
(1) 20mL 0.02molL is configured-1Cetyl trimethylammonium bromide be placed in the autoclave of 25mL, Stirring 5 minutes.
(2) 0.09165g H is weighed3BO3、0.3418g BeSO4, 0.1492g NaF be added step (1) in reaction kettle In, it is stirred on magnetic stirring apparatus to being completely dissolved.
(3) in the solution whipping process of step (2), 1molL is constantly added dropwise-1NaOH solution adjusts pH value of solution 12, continue stirring 15 minutes, is uniformly mixed solution.
(4) autoclave of step (3) mixed solution is put into baking oven, is reacted for 24 hours in 200 DEG C of baking ovens.Instead It is cooled to room temperature after should stopping, arrest reaction kettle outwells supernatant, and the white for washing bottom with ethyl alcohol and deionized water is heavy It forms sediment, washs until neutrality, centrifugation obtains product.Product is dried in 85 DEG C of baking ovens for 24 hours to get nonlinear optical crystal material Expect NBBF.TEM Electronic Speculum meets target product as shown in fig. 7, for banded structure.
Embodiment 7
(1) 20mL 0.06molL is configured-1Cetyl trimethylammonium bromide be placed in the autoclave of 25mL, Stirring 5 minutes.
(2) 0.09165g H is weighed3BO3、0.3418g BeSO4, 0.1492g NaF be added step (1) in reaction kettle In, it is stirred on magnetic stirring apparatus to being completely dissolved.
(3) in the solution whipping process of step (2), 1molL is constantly added dropwise-1NaOH solution adjusts pH value of solution 12, continue stirring 15 minutes, is uniformly mixed solution.
(4) autoclave of step (3) mixed solution is put into baking oven, reacts 3d in 200 DEG C of baking ovens.Reaction It being cooled to room temperature after stopping, arrest reaction kettle outwells supernatant, the white precipitate of bottom is washed with ethyl alcohol and deionized water, Until neutrality, centrifugation obtains product for washing.Product is dried in 85 DEG C of baking ovens for 24 hours to get non-linear optical crystal material NBBF.TEM Electronic Speculum meets target product as shown in figure 8, for banded structure.
Embodiment 8
(1) 20mL 0.02molL is configured-1Polyethylene glycol be placed in the autoclave of 25mL, stir 5 minutes.
(2) 0.09165g H is weighed3BO3、0.3418g BeSO4, 0.1492g NaF be added step (1) in reaction kettle In, it is stirred on magnetic stirring apparatus to being completely dissolved.
(3) in the solution whipping process of step (2), 1molL is constantly added dropwise-1NaOH solution adjusts pH value of solution 12, continue stirring 15 minutes, is uniformly mixed solution.
(4) autoclave of step (3) mixed solution is put into baking oven, is reacted for 24 hours in 200 DEG C of baking ovens.Instead It is cooled to room temperature after should stopping, arrest reaction kettle outwells supernatant, and the white for washing bottom with ethyl alcohol and deionized water is heavy It forms sediment, washs until neutrality, centrifugation obtains product.Product is dried in 85 DEG C of baking ovens for 24 hours to get nonlinear optical crystal material Expect NBBF.TEM Electronic Speculum meets target product as shown in figure 9, for banded structure.
Embodiment 9
(1) 20mL 0.06molL is configured-1Polyethylene glycol be placed in reaction kettle, stir 5 minutes.
(2) 0.09165g H is weighed3BO3、0.3418g BeSO4, 0.1492g NaF be added step (1) in reaction kettle In, it is stirred on magnetic stirring apparatus to being completely dissolved.
(3) in the solution whipping process of step (2), 1molL is constantly added dropwise-1NaOH solution adjusts pH value of solution 12, continue stirring 15 minutes, is uniformly mixed solution.
(4) autoclave of step (3) mixed solution is put into baking oven, reacts 3d in 200 DEG C of baking ovens.Reaction It being cooled to room temperature after stopping, arrest reaction kettle outwells supernatant, the white precipitate of bottom is washed with ethyl alcohol and deionized water, Until neutrality, centrifugation obtains product for washing.Product is dried in 85 DEG C of baking ovens for 24 hours to get non-linear optical crystal material NBBF.TEM Electronic Speculum is as shown in Figure 10, is banded structure, meets target product.
Embodiment 10
Electrode material using the NBBF material 0.035mg synthesized in embodiment 1 as lithium ion battery, with 0.5C (1C =140mAh/g) rate charge-discharge, and loop test 20 times, test result is as shown in figure 11, it is found that the material charge and discharge are imitated Fruit variation less, illustrates that the electrochemical stability of the material is good.Efficiency for charge-discharge under 20 cycle-indexes, test result is such as Shown in Figure 12, recycling 20 behind efficiencies is 98.9%.
The foregoing is merely preferred embodiment of the present disclosure, are not limited to the disclosure, for the skill of this field For art personnel, the disclosure can have various modifications and variations.It is all within the spirit and principle of the disclosure, it is made any to repair Change, equivalent replacement, improvement etc., should be included within the protection scope of the disclosure.

Claims (10)

1. a kind of preparation method of non-linear optical crystal material, characterized in that prepare NBBF, In using low-temperature hydrothermal synthetic method Surfactant, the ratio of the concentration in the reaction time and surfactant of low-temperature hydrothermal synthesis are added in low-temperature hydrothermal synthetic system Example is not less than 12:0.01, h:molL-1
2. the preparation method of non-linear optical crystal material as described in claim 1, characterized in that step are as follows:
By H3BO3、BeSO4, NaF be added into surfactant solution, adjust pH be 11.5~12.5, under confined conditions, heating It is reacted to 200~220 DEG C.
3. the preparation method of non-linear optical crystal material as described in claim 1, characterized in that H3BO3、BeSO4, NaF Molar ratio is 1:2.0~2.3:2.0~2.5.
4. the preparation method of non-linear optical crystal material as described in claim 1, characterized in that the concentration of surfactant For 0.02~0.06molL-1, the reaction time is 1~3 day.
5. the preparation method of non-linear optical crystal material as described in claim 1, characterized in that the material removal after reaction Supernatant liquor, by the dry acquisition non-linear optical crystal material of washing of precipitate.
6. the preparation method of non-linear optical crystal material as claimed in claim 5, characterized in that successively using second alcohol and water Washing;
Or, dry temperature is 80~90 DEG C, drying time is 22~26h.
7. the preparation method of non-linear optical crystal material as described in claim 1, characterized in that the surfactant is Lauryl sodium sulfate, polyethylene glycol or dodecyl trimethyl ammonium bromide.
8. the nonlinear optics that a kind of preparation method of any non-linear optical crystal material of claim 1~7 obtains Crystalline material.
9. a kind of application of non-linear optical crystal material according to any one of claims 8 in electrochemical field.
10. a kind of electrode material, characterized in that including non-linear optical crystal material according to any one of claims 8.
CN201910688550.XA 2019-07-29 2019-07-29 A kind of non-linear optical crystal material and preparation method and application Pending CN110424048A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201910688550.XA CN110424048A (en) 2019-07-29 2019-07-29 A kind of non-linear optical crystal material and preparation method and application

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201910688550.XA CN110424048A (en) 2019-07-29 2019-07-29 A kind of non-linear optical crystal material and preparation method and application

Publications (1)

Publication Number Publication Date
CN110424048A true CN110424048A (en) 2019-11-08

Family

ID=68412857

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201910688550.XA Pending CN110424048A (en) 2019-07-29 2019-07-29 A kind of non-linear optical crystal material and preparation method and application

Country Status (1)

Country Link
CN (1) CN110424048A (en)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1928167A (en) * 2005-09-06 2007-03-14 中国科学院福建物质结构研究所 Big-size potassium fluorine boron beryllium crystal, its growing in hydro-thermal method and frequency-converter
CN101050547A (en) * 2006-04-07 2007-10-10 中国科学院理化技术研究所 Method for developing potassium fluoroboric beryllium acid / sodium crystal through hydrothermal method
CN101200809A (en) * 2006-12-12 2008-06-18 中国科学院理化技术研究所 Method for synthesizing beryllium fluoroborate single-phase polycrystalline powder
CN101591800A (en) * 2009-06-11 2009-12-02 山东师范大学 A kind of method of preparing nonlinear optical crystal by using low temperature hydrothermal
CN104451859A (en) * 2014-10-28 2015-03-25 西安建筑科技大学 Method and device thereof for growing fluoro-boron beryllium kalium crystal

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1928167A (en) * 2005-09-06 2007-03-14 中国科学院福建物质结构研究所 Big-size potassium fluorine boron beryllium crystal, its growing in hydro-thermal method and frequency-converter
CN101050547A (en) * 2006-04-07 2007-10-10 中国科学院理化技术研究所 Method for developing potassium fluoroboric beryllium acid / sodium crystal through hydrothermal method
CN101200809A (en) * 2006-12-12 2008-06-18 中国科学院理化技术研究所 Method for synthesizing beryllium fluoroborate single-phase polycrystalline powder
CN101591800A (en) * 2009-06-11 2009-12-02 山东师范大学 A kind of method of preparing nonlinear optical crystal by using low temperature hydrothermal
CN104451859A (en) * 2014-10-28 2015-03-25 西安建筑科技大学 Method and device thereof for growing fluoro-boron beryllium kalium crystal

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
SHU GUO,ET AL.: "Deep-ultraviolet nonlinear optical crystal NaBe2BO3F2—Structure, growth and optical properties", 《JOURNAL OF CRYSTAL GROWTH》 *
陆剑波: "锂离子电池正极材料LiNi1/3Co1/3Mn1/3O2的形貌调控及其电化学性能研究", 《中国优秀硕士学位论文全文数据库 工程科技Ⅱ辑》 *
马惠云: "功能材料的设计与合成", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 *

Similar Documents

Publication Publication Date Title
Smith et al. Precision measurements of the coulombic efficiency of lithium-ion batteries and of electrode materials for lithium-ion batteries
CN110226252B (en) Polyanion type sodium ion battery positive electrode material and preparation method thereof
CN103430364B (en) The preparation method of slurry, the preparation method of solid electrolyte layer, the preparation method of electrode active material layers and all-solid-state battery
CN102760876B (en) Niobate and niobate composite material and application of niobate composite material to secondary lithium battery
CN107069020A (en) A kind of preparation method of lithium ion battery nickel doping vanadic anhydride nano-sheet positive electrode
CN103594685B (en) A kind of preparation method of modification of lithium ion battery anode material molybdenum trioxide
CN107240690A (en) A kind of preparation method of cladded type ternary cathode material of lithium ion battery
CN109390553A (en) Composite positive pole, positive plate and solid lithium battery
CN106099083A (en) The cladded type nickel ion doped material of a kind of hydro-thermal method surface modification, lithium battery and preparation method thereof
CN106299356B (en) A kind of lithium ion battery lithium vanadate Li3VO4The efficient microwave radiation synthesis process of nano flower
CN104810513B (en) A kind of lithium ion battery negative material and preparation method thereof
CN110534721B (en) Method for repairing ternary cathode material with degraded performance and ternary cathode material obtained by same
CN107170969B (en) A kind of lithium ion battery lithium-rich manganese base of modification and preparation method thereof
CN110424048A (en) A kind of non-linear optical crystal material and preparation method and application
CN103151518A (en) Coating technology of lithium cobalt oxide
CN102701280B (en) Preparation method of anode material of lithium ion battery
CN107492647A (en) Lithium ion battery negative material, cathode material preparation method and lithium ion battery
CN106809879A (en) A kind of niobium pentoxide nano stick material with regular hollow quadratic box-like and its preparation method and application
CN106673065A (en) Inorganic non-metallic material sodium manganese molybdate and preparation method and application thereof
CN105576228A (en) Method for preparing lithium manganate to serve as lithium-ion battery by sol-gel method
CN106058239B (en) A kind of preparation method of nanometer of linear lithium-rich manganese-based anode material
CN107732223A (en) Water system sodium-ion battery positive electrode and preparation method thereof and battery
CN114180627A (en) Sodium-ion battery positive electrode material and preparation method thereof, and sodium-ion battery
CN103964492B (en) GeOx material, preparation method thereof and application of GeOx material in lithium ion battery
CN106229500B (en) A kind of LiMn2O4 base anode material of high-temperature long life type non-stoichiometric and preparation method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication
RJ01 Rejection of invention patent application after publication

Application publication date: 20191108