CN107240678A - A kind of preparation method of lithium ion battery metal sulfide negative material - Google Patents
A kind of preparation method of lithium ion battery metal sulfide negative material Download PDFInfo
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- CN107240678A CN107240678A CN201610183514.4A CN201610183514A CN107240678A CN 107240678 A CN107240678 A CN 107240678A CN 201610183514 A CN201610183514 A CN 201610183514A CN 107240678 A CN107240678 A CN 107240678A
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- 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
- H01M4/362—Composites
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- 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
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- 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
- H01M4/581—Chalcogenides or intercalation compounds thereof
- H01M4/5815—Sulfides
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- 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 present invention relates to a kind of preparation method of lithium ion battery with metal sulfide negative material, the lithium ion battery sulfide of the metal sulfide negative material comprising metal M or metal M sulfide and the composite of additive A formation, metal M is at least one of Fe, Sc, Ti, Cr, Mn, Co, Ni, Cu, Zn, Y, Zr, Hf, Mo, Er, In, Ga, Ge, Sn, Ru, Ta, La, W, Nb, Pd and Pt, and additive A is graphene, CNT, metal organic framework, SiO2、Al2O3At least one of and polymer.Preparation method is simple in the present invention, moderate cost, it is easy to commercialization generation, helps to promote application of the metal sulfide in terms of sulphion cell negative electrode material.
Description
Technical field
The present invention relates to preparation method of the lithium ion battery with metal sulfide negative material, belong to new material synthesis field.
Background technology
Since 21 century, environmental pollution and energy shortage problem say beneficial serious, in the urgent need to developing various fuel
Battery and high-energy battery, wherein Development of EV are the task of top priority, and the key of electric automobile is then battery, and wherein lithium from
Sub- battery is considered as that can most meet one of high-energy battery of future society sustainable development requirement again.With other secondary cell phases
Than lithium ion battery has operating voltage height, specific energy height, good security, memory-less effect, self discharge small, dirty without environment
The advantages of dye[1-8].In recent years, lithium ion battery have developed rapidly, and be widely used for mobile phone, digital camera, notebook electricity
The portable electric appts such as brain, MP3, video camera and space flight, aviation field, and greatly weighed in electric automobile field
Depending on.Therefore, the industry that various lithium ion battery for electric vehicle will be given priority to as various countries from now on, while being also China's power electric
Pond industry development opens more wide demand space.
However, current lithium ion battery can not also meet the energy density demand of sustainable growth, such as pure electric vehicle and mixing
Electric car.This develops the battery material of high-energy-density, high rate capability with regard to active demand so that the energy of lithium ion battery is close
Degree and power density meet current demand, and then promote the fast development of ev industry.Negative material is influence lithium-ion electric
One of critical material of pond performance.Early stage lithium ion battery negative material uses lithium metal.But due to the activity of elemental lithium
Greatly, in discharge and recharge, the out-of-flatness of surface of metal electrode makes the skewness of its surface potential, and easily dendrite is formed in charging
Key, causes short circuit, electric leakage even to be exploded, this is caused to the security of battery as the accumulation of dendrite lithium can puncture barrier film
Serious potential safety hazard.Therefore, the negative material that elemental lithium can be replaced and can be reacted with lithium by finding other turns into people
The emphasis studied.Preferable lithium ion battery negative material usually requires to meet following condition：(1) lithium it is embedding-dealkylation reaction
During, current potential is low and current potential very close to lithium metal, to ensure that battery has higher and stable output voltage；(2)
With higher electrochemistry capacitance and higher efficiency for charge-discharge, to ensure that battery has higher energy density and less capacity
Loss；(3) in the inside and surface of electrode material, lithium ion has faster diffusion rate, to ensure the power of electrode process
Factor, so that battery can be with higher rate charge-discharge, the need for meeting power type power supply；(4) there is good conduction
Property；(5) there is higher structural stability, chemical stability and heat endurance, do not reacted with electrolyte, to ensure electricity
Pond has good cycle performance；(6) processability of electrode will get well；(7) it is easy to prepare, and aboundresources is cheap, right
Environmental nonpollution.[9]Current lithium ion battery negative material mainly have graphite, amorphous carbons, CNT, silica-base material,
Tin-based material, alloy material, transition metal oxide and two-dimension nano materials.
Graphene is the monolayer compound of carbon, and its unique two-dimensional structure causes the great interest of people.Due to stone
Black alkene is that graphite is stripped into monoatomic layer and obtained, then the lamellar structure compound of other similar graphite, such as MoS2、WS2
Deng monoatomic layer structure perhaps can be separated by method chemically or physically, and we are referred to as this kind of individual layer or few Rotating fields
" class graphene " structure (Graphene-like, GL).And transient metal sulfide is equally attract attention, particularly
Some have the class graphene transient metal sulfide MS of layer structure2(M=Ti, Nb, Ta, Mo, W etc.).This kind of tool
There is the sulfide of the layer structure of quasi- two dimension, be typical three layers structure, i.e., a metal is clipped between two S layers
M (M=Mo, W) layer.In crystal structure, in S-M-S layers, each M atoms are hexa-coordinate in octahedron, and M-S is former
It is covalent bond between son, is connected between layers with weak Van der Waals force.This structure to be good for effect in compound middle level by force, and
The interaction force of interlayer is relatively weak, and the space of interlayer can allow that foreign substance enters.[10]This kind of stratiform Transition Metal Sulfur
Compound is that can provide good lithium ion diffusion admittance as ion cathode material lithium biggest advantage, and buffering removal lithium embedded is that occur
Volumetric expansion, the stable cycle performance and high rate capability of battery are most promising lithium ion battery negative materials preferably
One of.
But the method for synthesis metal sulfide that document has been reported now the problem of exist including following two aspects：(1) close
Into metal sulfide be bulk material, it is necessary to further liquid phase method peel off generation stratified material；(2) synthesized using hydro-thermal method
Metal sulfide pattern is uneven.
Bibliography:
[1]Liang Y,Ji L,Guo B,Lin Z,Yao Y,Li Y,et al.Preparation and electrochemical characterization
of ionic-conducting lithium lanthanum titanate oxide/polyacrylonitrile submicron composite fiber-
based lithium-ion battery separators.J Power Sources,2011,196(1):436-44I.
[2]Liu H,Wang Y,Wang K,Wang Y,Zhou H.Synthesis and electrochemical properties of single-
crystalline LiV3O8 nanorods as cathode materials for rechargeable lithium batteries.J Power
Sources,2009,192(2):668-673.
[3]Yaakov D,Gofer Y,Aurbach D,Halalay IC.On the study of electrolyte solutions for li-ion
batteries that can work over a wide temperature range.J Electrochem Soc.,2010,157(12):A1383-
A1391.
[4]Yamada I,Mukai SR.The effect of porous structure on the li insertion/extraction behavior of
carbon gel microspheres encasing silicon powder.Electrochemistry,2010,78(5):393-396.
[5]Yi TF,Zhu YR,Zhu XD,Shu J,Yue CB,Zhou AN.A review of recent developments in the
surface modification of LiMnsO；as cathode material of power lithium-ion battery.Ionics,2009,
15(6):79-784.
[6]Zhang LQ,Liu XH,Liu Y,Huang S,Zhu T,Gui LJ,et al.Controlling the lithiation-induced
strain and charging rate in nanowire electrodes by coating.ACS Nano.,2011,5(6):4800-4809.
[7]Zukowska GZ,Marcinek M,Drzewiecki S,Kryczka J,Syzdek J,Adamczyk-Wozniak A,et
al.Studies on the influence of tris(pentafluorophenyl)borane on the properties of ethylene carbonate,
dimethyl carbonate and poly(ethylene oxide)dimethyl ether lithium trifluoromethanesulfonate
electrolytes.J Power Sources,2010,195(22):7506-7510.
[8]Zuo P,Yin G,Yang Z,Wang Z,Cheng X,Jia D,et al.Improvement of cycle performance for
silicon/carbon composite used as anode for lithium ion batteries.Materials Chemistry and Physics,
2009,115(2-3):757-760.
[9] the full Unit sources precursor process of Sun Ji prepares oxide and sulfide nano-material Jiangsu Universitys, 2009.
[10] Chen Guang, Zhao Xiuyun, Xia Ding state secondary lithium battery sulphur system positive electrode progress new material industries, 2010,
10:15-19.。
The content of the invention
For above mentioned problem, it is an object of the invention to provide one kind have the uniform lithium ion battery metal sulfide of pattern
Negative material and preparation method.
In order to solve the above-mentioned technical problem, the invention provides a kind of system of lithium ion battery with metal sulfide negative material
Preparation Method, the lithium ion battery sulfide of the metal sulfide negative material comprising metal M or metal M sulfide
With additive A formation composite, metal M be Fe, Sc, Ti, Cr, Mn, Co, Ni, Cu, Zn, Y,
At least one of Zr, Hf, Mo, Er, In, Ga, Ge, Sn, Ru, Ta, La, W, Nb, Pd and Pt, addition
Agent A is graphene, CNT, metal organic framework (MOFs), SiO2、Al2O3And at least one in polymer
Kind, the preparation method includes：By metal M hydroxide or metal M hydroxide and additive A or addition
The compound of agent A presoma formation, mixes with elemental sulfur, is warming up in protective atmosphere at 300 DEG C -600 DEG C of holding temperature
Insulation 1-6 hours, obtains the lithium ion battery metal sulfide negative material.
The present invention generates metal sulfide using metal hydroxides with reaction of Salmon-Saxl, and the metal sulfide that the method is obtained is not only
The pattern of metal oxide can be kept, also with excellent stable circulation performance；Preparation method is simple in the present invention, and cost is fitted
In, it is easy to commercialization generation, help to promote application of the metal sulfide in terms of sulphion cell negative electrode material.
In the example of the present invention, the lithium ion battery includes metal M vulcanization with metal sulfide negative material
Thing, the hydroxide of the metal M is prepared by following methods：Metal M salt, urea and water are mixed, at room temperature
Stirring centrifuges, cleaned and dry, obtain the hydrogen of the metal M after being reacted 8-24 hours at 80-200 DEG C for 0.5-3 hours
Oxide.
In another example of the present invention, the lithium ion battery includes metal M sulphur with metal sulfide negative material
Compound and the composite of additive A formation, the hydroxide and the presoma of additive A or additive A of the metal M
The compound of formation is prepared by following methods：By metal M salt, additive A or the presoma, urea and the water that add A
Mix, ultrasound centrifuges, cleaned and dry, obtain institute after being reacted 8-24 hours at 80-200 DEG C for 3-5 hours at room temperature
State the compound of metal M hydroxide and the presoma formation of additive A or additive A.
The method of the present invention prepares metal hydroxides as the presoma of metal sulfide using hydro-thermal method first, so makes
Standby metal sulfide and the pattern of reservation metal hydroxides, and preparation method is easy, is adapted to large-scale production.
It is preferred that the salt of the metal M is at least one in metal M nitrate, chloride, acetate, sulfate
Kind.
It is preferred that the salt of the metal M and the mol ratio of urea are 1:(1~10), preferably 1:1.25.
It is preferred that the salt of the metal M is 1 with additive A or the mol ratio of the presoma of additive A:(1~10),
It is preferred that 1:6.7.
It is preferred that the mass ratio of the metal hydroxides and elemental sulfur is 1:(1~5), preferably 1:2.
It is preferred that the protective atmosphere is Ar and N2In any one.
It is preferred that the present invention is warming up to 300 DEG C -600 DEG C of holding temperature with 1-10 DEG C/min.
The present invention has the following aspects remarkable advantage：
1), the present invention obtains the metal hydroxides of different-shape structure using hydro-thermal method, it is vulcanized with sulphur in-situ preparation metal
Thing, the metal sulfide that the method is obtained can not only keep the pattern of metal oxide, also with excellent cyclical stability
Energy；
2), preparation method is simple in the present invention, moderate cost, it is easy to commercialization generation, helps to promote metal sulfide in sulphion
Application in terms of cell negative electrode material.
Brief description of the drawings
Fig. 1 is the part metals sulfide (MS that embodiment 1-8 is synthesizedn, M=Mn, Fe, Co, Ni, Cu, Zn, In) material
XRD spectrum；
Fig. 2 is the Ni (OH) that embodiment 8 is synthesized2The TEM figures of-Graphene and NiS-Graphene materials；
The cycle performance for the CoS-Graphene composites that Fig. 3 is the NiS-Graphene that embodiment 8 is synthesized and embodiment 9 is synthesized
Figure.
Embodiment
Implementation below further illustrates the present invention, it should be appreciated that following embodiments are merely to illustrate the present invention, rather than
The limitation present invention.
The present invention directly prepares metal sulfide as lithium ion battery metal sulphur by the use of metal hydroxides and elemental sulfur
Compound negative material.The chemical composition of the metal sulfide of formation can be MSn, wherein, M can for Fe, Sc, Ti, Cr,
Mn、Co、Ni、Cu、Zn、Y、Zr、Hf、Mo、Er、In、Ga、Ge、Sn、Ru、Ta、La、W、Nb、
At least one of Pd and Pt.It should be understood that n value depends on metal M valence state, and same metal may also be due to tool
There is different valence state and there is different n values, such as MSnCan be Fe9S10、MnS、Co9S8、Ni3S2、NiS、Cu1.81S、
CuS2、In2S3Deng.
Metal hydroxides is mixed with elemental sulfur, is warming up in protective atmosphere at 300 DEG C -600 DEG C of holding temperature and is incubated 1-
6 hours, obtain the lithium ion battery metal sulfide negative material.The mass ratio that feeds intake of metal hydroxides and elemental sulfur can
For 1:(1~5), preferably 1:2, heating rate can be 1-10 DEG C/min.Protective atmosphere used can be Ar and N2In it is any one
Kind.
The method of the present invention prepares metal M sulfide and the composite of additive A formation as lithium ion battery gold
Belong to sulfide negative material.Wherein additive A can be but to be not limited only to graphene (Grahene), CNT, metal organic
Skeleton (MOFs), SiO2、Al2O3, at least one of polymer (Polymer).
Metal oxide used in the present invention can be made using hydro-thermal method, and the gold of different-shape structure is can obtain using hydro-thermal method
Belong to hydroxide, it is generated metal sulfide with simple substance reaction of Salmon-Saxl.The metal sulfide that the present invention is obtained can not only be protected
The pattern of metal oxide is held, but also with excellent stable circulation performance.The present invention is by calcining metal hydroxide
Sulphur is added during preparing metal-oxide makes its in-situ preparation metal sulfide, so allows for the synthesis of metal sulfide
It is easy as metal oxide, help to promote application of the metal sulfide in terms of sulphion cell negative electrode material.
Metal hydroxides can be prepared using metal salt and urea as raw material, specifically, metal salt, urea and water are mixed,
0.5-3 hours are stirred at room temperature after being reacted 8-24 hours at 80-200 DEG C, centrifuged, are cleaned and dry, can obtain metal
Hydroxide.Wherein, the metal salt can be but be not limited only in M nitrate, chloride, acetate, sulfate
It is at least one.The mol ratio of the metal salt and urea can be 1:(1~10), preferably 1:1.25.
If composite also includes above-mentioned additive A, additive A, Ke Yizhi can be added when preparing metal hydroxides
Connect additive A and to mix ultrasonically treated 3-5 hours with metal salt, urea and water, 8-24 is then reacted at 80-200 DEG C small
When, centrifuge, clean and dry, obtain metal hydroxides composite.For example, when additive is graphene, its forerunner
Body can select graphene oxide.Metal salt can be 1 with the additive A or the mol ratio of addition A presoma added:(1~
10), preferably 1:6.7.
Being assembled into half-cell as negative material by metal sulfide made from the method for the present invention, (electrolyte is LiPF6)
Afterwards, in 100mAh g-1It is lower to remain to maintain higher charge/discharge capacity after the discharge and recharge of tens times (referring to Fig. 3).
Embodiment is enumerated further below to describe the present invention in detail.It will similarly be understood that following examples are served only for this hair
It is bright to be further described, it is impossible to be interpreted as limiting the scope of the invention, those skilled in the art is according to the present invention's
Some nonessential modifications and adaptations that the above is made belong to protection scope of the present invention.Following specific technique ginsengs of example
Number etc. is also only an example in OK range, i.e. those skilled in the art can be done in suitable scope by this paper explanation
Selection, and do not really want to be defined in the concrete numerical value of hereafter example.
Embodiment 1
1. metal hydroxides Mn (OH)2Preparation
By 1mmol Mn (NO3)2It is fitted into reactor, adds 0.1g urea and 50mL distilled water, solution is first in room
Temperature stirring 1 hour, finally reactor is positioned in 80-200 DEG C of oil bath react 8-24 hour, react terminate after from
The heart, using washes of absolute alcohol 3 times, Mn (OH) is obtained after 65 DEG C of drying2；
2. the preparation of metal sulfide material
By 0.2g Mn (OH)2Uniformly mixed with 0.2g sulphur powder, in Ar gas shielded atmosphere, with 1-10 DEG C/min from room temperature
It is heated to 300-600 DEG C and is incubated 1-6 hours, cooling can obtains MnS.
Embodiment 2
Repeat embodiment 1 but with Fe (SO4)2Instead of Mn (NO3)2Fe (OH) is made2Fe is made with sulphur powder reaction again9S10。
Embodiment 3
Repeat embodiment 1 but with Co (NO3)2Instead of Mn (NO3)2Co (OH) is made2Co is made with sulphur powder reaction again9S8。
Embodiment 4
Repeat embodiment 1 but with Ni (NO3)2Instead of Mn (NO3)2Ni (OH) is made2Ni is made with sulphur powder reaction again3S2。
Embodiment 5
Repeat embodiment 1 but with Cu (NO3)2Instead of Mn (NO3)2Cu (OH) is made2Cu is made with sulphur powder reaction againaSb, through XRD
Analysis display, contains Cu1.98S and CuS2。
Embodiment 6
Repeat embodiment 1 but with ZnCl2Instead of Mn (NO3)2Zn (OH) is made2ZnS is made with sulphur powder reaction again.
Embodiment 7
Repeat embodiment 1 but with In (NO3)3Instead of Mn (NO3)2In (OH) is made3In is made with sulphur powder reaction again2S3。
Embodiment 8
1.GO-Ni(OH)2(graphene oxide-Ni (OH)2) material preparation
By 1mmol Ni (NO3)2It is fitted into 80mg graphene oxide (GO) in reactor, adds 0.1g urea and 50
ML distilled water, solution in room temperature ultrasound 3-5 hours, obtains the solution of black, reactor finally is positioned over into 80- first
Reacted 8-24 hour in 200 DEG C of oil bath, reaction is centrifuged after terminating, using washes of absolute alcohol 3 times, be after 65 DEG C of drying
Obtain GO-Ni (OH)2；
The preparation of 2.NiS- grapheme materials
By 0.2g GO-Ni (OH)2Uniformly mixed with 0.1g sulphur powder, in Ar gas shielded atmosphere, with 1-10 DEG C/min from room
Temperature is heated to 300-600 DEG C and is incubated 1-6 hours, produces NiS- graphene composite materials.
Embodiment 9
Repeat embodiment 8 but with Co (NO3)2Instead of Ni (NO3)2GO-Co (OH) is made2CoS- graphenes are made with sulphur powder reaction again
Material.
Fig. 1 is the part metals sulfide (MS that embodiment 1-8 is synthesizedn, M=Mn, Fe, Co, Ni, Cu, Zn, In) material
XRD spectrum.
As negative material the metal sulfide of above-mentioned preparation is assembled into half-cell, and (electrolyte is LiPF6) after,
100mA h g-1It is lower to remain to maintain higher charge/discharge capacity after the discharge and recharge of tens times (referring to Fig. 3).Fig. 3 is implementation
The cycle performance figure for the NiS- graphene composite materials that the CoS- graphene composite materials and embodiment 8 that example 9 is synthesized are synthesized.From
Understand that CoS- graphene composite materials show good cyclical stability in Fig. 3,600mAh is still kept after 80 circulations
g-1Capacity.(a) is the Ni (OH) that embodiment 8 is synthesized in Fig. 22The TEM figures of-graphene composite material, (b) is real
Apply the TEM figures of the NiS- graphene composite materials of the synthesis of example 8.NiS in NiS- graphene composite materials as can be known from Fig. 2
Still keep the pattern of hexagon, and without obvious agglomeration, this pattern be conducive in electro-chemical test with electrolyte
Contact.
As negative material the metal sulfide of above-mentioned preparation is assembled into half-cell, and (electrolyte is LiPF6) after,
100mA h g-1It is lower to remain to maintain higher charge/discharge capacity after the discharge and recharge of tens times (referring to Fig. 3).In Fig. 3 (a)
The CoS- graphene composite material cycle performance figures synthesized for embodiment 9, (b) is that the NiS- graphenes that embodiment 8 is synthesized are answered
The cycle performance figure of condensation material.CoS- graphene composite materials show good cyclical stability, 80 times as can be known from Fig. 3
600mAh g are still kept after circulation-1Capacity.
Claims (9)
1. a kind of lithium ion battery preparation method of metal sulfide negative material, it is characterized in that, the lithium ion battery sulfide of the metal sulfide negative material comprising metal M or metal M sulfide and the composite of additive A formation, metal M is at least one of Fe, Sc, Ti, Cr, Mn, Co, Ni, Cu, Zn, Y, Zr, Hf, Mo, Er, In, Ga, Ge, Sn, Ru, Ta, La, W, Nb, Pd and Pt, and additive A is graphene, CNT, metal organic framework, SiO2、Al2O3At least one of and polymer, the preparation method includes：By metal M hydroxide or metal M hydroxide and the compound of the presoma of additive A or additive A formation; mixed with elemental sulfur; it is warming up in protective atmosphere at 300 DEG C~600 DEG C of holding temperature and is incubated 1~6 hour, obtains the lithium ion battery metal sulfide negative material.
2. preparation method according to claim 1, it is characterised in that the lithium ion battery includes metal M sulfide with metal sulfide negative material, the hydroxide of the metal M is prepared by following methods:Metal M salt, urea and water are mixed, 0.5~3 hour is stirred at room temperature after being reacted 8~24 hours at 80~200 DEG C, centrifuges, clean and dry, obtain the hydroxide of the metal M.
3. preparation method according to claim 1, it is characterized in that, the lithium ion battery sulfide of the metal sulfide negative material comprising metal M and the composite of additive A formation, the hydroxide of the metal M and the compound of the presoma formation of additive A or additive A are prepared by following methods:Metal M salt, additive A or the presoma, urea and water that add A are mixed, at room temperature ultrasound 3~5 hours after at 80~200 DEG C react 8~24 hours, centrifuge, clean and dry, obtain the compound of the hydroxide of the metal M and the presoma formation of additive A or additive A.
4. the preparation method according to Claims 2 or 3, it is characterised in that the salt of the metal M is at least one of metal M nitrate, chloride, acetate, sulfate.
5. the preparation method according to Claims 2 or 3, it is characterised in that the salt of the metal M and the mol ratio of urea are 1:（1~10), preferably 1:1.25.
6. preparation method according to claim 3, it is characterised in that the salt of the metal M is 1 with additive A or the mol ratio of the presoma of additive A:（1~10), preferably 1:6.7.
7. the preparation method according to any one of claim 1-6, it is characterised in that the mass ratio of the metal hydroxides and elemental sulfur is 1:（1~5), preferably 1:2.
8. the preparation method according to any one of claim 1-7, it is characterised in that the protective atmosphere is Ar and N2In any one.
9. the preparation method according to any one of claim 1-8, it is characterised in that be warming up to 300 DEG C~600 DEG C of holding temperature with 1~10 DEG C/min.
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| CN108091875A (en) * | 2017-12-29 | 2018-05-29 | 暨南大学 | A kind of Prussian blue derivative iron-cobalt-nickel sulfide and preparation method and application |
| CN108091875B (en) * | 2017-12-29 | 2020-05-08 | 暨南大学 | Prussian blue derived iron-cobalt-nickel sulfide and preparation method and application thereof |
| CN110407165A (en) * | 2018-04-27 | 2019-11-05 | 宝山钢铁股份有限公司 | The covalent organic framework that lithium-sulfur cell is adulterated with selenium-sulphur anode composite material and its synthetic method |
| CN110957146A (en) * | 2019-11-12 | 2020-04-03 | 洛阳师范学院 | Preparation method of supercapacitor composite electrode material and electrode |
| CN110931754A (en) * | 2019-12-12 | 2020-03-27 | 宁德新能源科技有限公司 | Negative electrode material, preparation method thereof, negative electrode plate and electrochemical device |
| CN112467068A (en) * | 2020-12-11 | 2021-03-09 | 燕山大学 | Battery negative electrode material and preparation method and application thereof |
| CN112573530A (en) * | 2020-12-18 | 2021-03-30 | 四川大学 | Sulfur species activated SiO2Preparation method of lithium battery negative electrode material |
| CN112573530B (en) * | 2020-12-18 | 2022-08-05 | 四川大学 | Sulfur species activated SiO 2 Preparation method of lithium battery negative electrode material |
| CN114031108A (en) * | 2021-11-02 | 2022-02-11 | 远景动力技术(江苏)有限公司 | Composite sulfide and preparation method and application thereof |
| CN114031108B (en) * | 2021-11-02 | 2024-04-26 | 远景动力技术(江苏)有限公司 | Composite sulfide and preparation method and application thereof |
| CN114203965A (en) * | 2021-12-07 | 2022-03-18 | 远景动力技术(江苏)有限公司 | Electrochemical device and electronic apparatus |
| CN114203965B (en) * | 2021-12-07 | 2024-01-30 | 远景动力技术(江苏)有限公司 | Electrochemical device and electronic apparatus |
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