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 PDFInfo
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- 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
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- C30B—SINGLE-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
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/10—Inorganic compounds or compositions
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- C30—CRYSTAL GROWTH
- C30B—SINGLE-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
- C30B7/00—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions
- C30B7/10—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions by application of pressure, e.g. hydrothermal processes
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- H01M10/052—Li-accumulators
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- H—ELECTRICITY
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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
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.
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