CN109904417A - A lithium-dissimilar metal composite negative electrode material and preparation method thereof - Google Patents
A lithium-dissimilar metal composite negative electrode material and preparation method thereof Download PDFInfo
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- CN109904417A CN109904417A CN201910084743.4A CN201910084743A CN109904417A CN 109904417 A CN109904417 A CN 109904417A CN 201910084743 A CN201910084743 A CN 201910084743A CN 109904417 A CN109904417 A CN 109904417A
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- 239000002905 metal composite material Substances 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- 239000007773 negative electrode material Substances 0.000 title abstract description 17
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 177
- 239000002184 metal Substances 0.000 claims abstract description 76
- 229910052751 metal Inorganic materials 0.000 claims abstract description 72
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 68
- 239000000463 material Substances 0.000 claims abstract description 60
- 239000000956 alloy Substances 0.000 claims abstract description 57
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 56
- 238000002844 melting Methods 0.000 claims abstract description 31
- 230000008018 melting Effects 0.000 claims abstract description 31
- 238000010438 heat treatment Methods 0.000 claims abstract description 23
- 239000000126 substance Substances 0.000 claims abstract description 9
- 239000011575 calcium Substances 0.000 claims description 33
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 22
- 229910052791 calcium Inorganic materials 0.000 claims description 21
- 239000011777 magnesium Substances 0.000 claims description 12
- 229910052788 barium Inorganic materials 0.000 claims description 8
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 8
- 239000011135 tin Substances 0.000 claims description 7
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 6
- 229910052749 magnesium Inorganic materials 0.000 claims description 6
- 239000010703 silicon Substances 0.000 claims description 6
- 229910052710 silicon Inorganic materials 0.000 claims description 6
- 229910052712 strontium Inorganic materials 0.000 claims description 6
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 6
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 4
- 239000004411 aluminium Substances 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052787 antimony Inorganic materials 0.000 claims description 4
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 4
- 229910052797 bismuth Inorganic materials 0.000 claims description 4
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 4
- 229910052738 indium Inorganic materials 0.000 claims description 4
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 4
- 229910001092 metal group alloy Inorganic materials 0.000 claims description 4
- 229910052718 tin Inorganic materials 0.000 claims description 4
- 239000011701 zinc Substances 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims 1
- 229910052725 zinc Inorganic materials 0.000 claims 1
- 239000010406 cathode material Substances 0.000 abstract description 16
- 229910000882 Ca alloy Inorganic materials 0.000 description 47
- USOPFYZPGZGBEB-UHFFFAOYSA-N calcium lithium Chemical compound [Li].[Ca] USOPFYZPGZGBEB-UHFFFAOYSA-N 0.000 description 47
- 238000000034 method Methods 0.000 description 16
- 210000001787 dendrite Anatomy 0.000 description 14
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- 239000003792 electrolyte Substances 0.000 description 8
- 230000005518 electrochemistry Effects 0.000 description 7
- 239000011888 foil Substances 0.000 description 7
- 238000002156 mixing Methods 0.000 description 6
- 229910006270 Li—Li Inorganic materials 0.000 description 5
- 210000004027 cell Anatomy 0.000 description 5
- 230000010287 polarization Effects 0.000 description 5
- 229910052786 argon Inorganic materials 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000000151 deposition Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 239000011889 copper foil Substances 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 238000004321 preservation Methods 0.000 description 3
- 229910001290 LiPF6 Inorganic materials 0.000 description 2
- 229910001297 Zn alloy Inorganic materials 0.000 description 2
- 229910000905 alloy phase Inorganic materials 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- CKFRRHLHAJZIIN-UHFFFAOYSA-N cobalt lithium Chemical compound [Li].[Co] CKFRRHLHAJZIIN-UHFFFAOYSA-N 0.000 description 2
- 239000006184 cosolvent Substances 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Inorganic materials [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 2
- KUJOABUXCGVGIY-UHFFFAOYSA-N lithium zinc Chemical compound [Li].[Zn] KUJOABUXCGVGIY-UHFFFAOYSA-N 0.000 description 2
- 238000001465 metallisation Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- SMBQBQBNOXIFSF-UHFFFAOYSA-N dilithium Chemical compound [Li][Li] SMBQBQBNOXIFSF-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000010410 dusting Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 150000002641 lithium Chemical group 0.000 description 1
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
Classifications
-
- 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
Landscapes
- Battery Electrode And Active Subsutance (AREA)
Abstract
A kind of lithium-dissimilar metal composite negative pole material and preparation method thereof, belongs to cell negative electrode material technical field.Firstly, making lithium metal become molten condition by heating lithium metal to 200~800 DEG C；Then, dissimilar metal is added in the lithium metal of molten condition, keeps the temperature 5~60min, be uniformly mixed, form the alloy of melting；Finally, molten alloy is cooled to room temperature, the lithium-dissimilar metal composite negative pole material can be obtained.The material contains metal lithium simple substance phase, as lithium cell cathode material in use, metal lithium simple substance mutually serves as lithium source.The present invention provides a kind of lithium-dissimilar metal composite negative pole materials and preparation method thereof, and simple possible is at low cost, which is applied in lithium battery that the coulombic efficiency and cycle life of battery can be effectively improved.
Description
Technical field
The invention belongs to cell negative electrode material technical fields, and in particular to a kind of lithium-dissimilar metal composite negative pole material and
Preparation method.
Background technique
People the battery energy density of electronic equipment, electric car etc. is required it is higher and higher, and lithium anode due to
With high specific capacity (3861mAh/g), minimum electrochemical potential (- 3.04V), lesser density (0.534g/cm3), it forms
For most promising high power lithium battery negative electrode material.Currently, the main problem that limitation lithium metal is applied in high-energy battery is
Dead lithium and lithium dendrite growth will lead to that coulombic efficiency is low, cycle life is short and the serious problems such as poor safety performance.Li dendrite and
The main reason for dead lithium formation is to cause in cyclic process since lithium metal deposition unevenly increases electrode surface roughness
The even formation Li dendrite of current distribution is uneven, while depositing/volume change of course of dissolution can make solid electrolyte interface film (SEI
Film) persistently rupture, causes the unstable of SEI film, the unstable generating rate for accelerating Li dendrite again in turn of SEI film.In addition,
Lithium filament will form dead lithium after electrode surface disengaging, and the formation of dead lithium will lead to lithium source loss, coulombic efficiency reduces, capacity declines
Subtract, stability decline and safety problem etc.；Simultaneously because the indeterminate growth of Li dendrite leads to the variation of volume, cause in material
Portion's stress variation, interface fluctuation and lithium electrode dusting, bring additional electrolyte consumption.
In order to inhibit the growth of Li dendrite, usually improved at present from electrolyte, diaphragm, surface modification etc..Separately
It is outer using three-dimensional structure as skeleton structure, the volume change in lithium anode charge and discharge process can also be effectively relieved, in turn
Inhibit Li dendrite.However, above method complex process, is not suitable for large-scale production and application, it is badly in need of at present a kind of simple and effective
Inhibition Li dendrite method.
Summary of the invention
In view of the defects in the background art, the present invention proposes a kind of lithium-dissimilar metal composite negative pole material and its systems
Preparation Method efficiently solves lithium anode material during circulating battery due to the growth bring coulombic efficiency of Li dendrite
Low, the problems such as service life is short.
The technical solution adopted by the present invention to solve the technical problems is as follows:
A kind of lithium-dissimilar metal composite negative pole material, including lithium simple substance phase and lithium-dissimilar metal alloy phase two phase structure,
Wherein, the molar ratio of lithium and dissimilar metal is (1~100): 1.
A kind of preparation method of lithium-dissimilar metal composite negative pole material, specifically includes the following steps:
Step 1, by heating lithium metal to 200~800 DEG C, make lithium metal become molten condition；
Dissimilar metal is added in the lithium metal for the molten condition that step 1 obtains step 2, keeps the temperature 5~60min, and mixing is equal
It is even, form the alloy of melting；Wherein, the dissimilar metal is magnesium (Mg), calcium (Ca), zinc (Zn), indium (In), aluminium (Al), tin
(Sn), at least one of silicon (Si), strontium (Sr), antimony (Sb), barium (Ba), lead (Pb), bismuth (Bi) are characterized in occur with lithium
Electrochemically alloying reaction, obtained lithium metal-dissimilar metal negative electrode material have two phase structure, i.e., metal lithium simple substance phase with
Lithium-dissimilar metal alloy phase；
Lithium metal is in a molten state, and temperature is less than the melting temperature of dissimilar metal；To the lithium metal of molten condition
After middle addition dissimilar metal, lithium metal can play the role of cosolvent, so that lithium metal and dissimilar metal are lower than xenogenesis in temperature
Also melting mixing can be carried out under the conditions of the melting temperature of metal well.When lithium metal melting temperature is higher, lithium metal with it is different
Molten alloy can be more quickly formed in kind metal；When melting temperature is suitable upon lowering, two kinds of metals also can be with slower speed shape
At molten alloy.And in 200~800 DEG C of temperature ranges proposed by the present invention, it is mixed to may make that lithium metal and dissimilar metal melt
It closes, forms molten alloy.
Step 3, the molten alloy for obtaining step 2 are cooled to room temperature, and the lithium-dissimilar metal composite negative pole can be obtained
Material.In the cooling procedure of molten alloy, dissimilar metal and part metals lithium form alloy phase (such as CaLi2Alloy phase),
Extra lithium metal then exists with simple substance form, and at room temperature, and uniform lithium metal alloy net is formd inside lithium-dissimilar metal
Network structure.Such composite construction is present among cell negative electrode material, can effectively improve the performance of battery.
Further, the molar ratio of dissimilar metal described in step 2 and lithium metal described in step 1 is 1:(1~100).
Further, the time that molten alloy is cooled to room temperature in step 3 is 1~10min.
Further, step 1 is to complete in glove box to step 3, i.e., is in dew point not higher than -50 DEG C, oxygen
What content was completed in the environment not higher than 10ppm.
The present invention also provides above-mentioned lithium-application of the dissimilar metal composite negative pole material in lithium battery.
The present invention provides a kind of lithium-dissimilar metal composite negative pole material and preparation method thereof, basic principles are as follows: first
First, heating lithium metal is formed into lithium molten state, then dissimilar metal is added in the lithium of molten state, at this point, lithium is as cosolvent,
So that lithium metal and dissimilar metal can also carry out melting mixing under the conditions of temperature is lower than dissimilar metal melting temperature well, obtain
To mixture be melting mixing alloy state, under microstructure, lithium atom and metallic atom are uniformly mixed, and work as temperature
During being cooled to room temperature, dissimilar metal such as calcium can form CaLi with lithium metal2Alloy, meanwhile, CaLi2Alloy forms net
Network structure, remaining lithium simple substance are filled in lithium calcium alloy CaLi2The inside of network structure, and be homogenously mixed together, shape
At compound.
Compared with prior art, the invention has the benefit that
1, the dissimilar metal of a kind of lithium-dissimilar metal composite negative pole material provided by the invention, selection can be sent out with lithium metal
The reaction of intercrescence gold, lithium-dissimilar metal alloy of formation are three dimensional skeletal structure, so that during charge and discharge cycles, only metal
Lithium simple substance mutually participates in electrochemical reaction, and the dissolution of lithium metal and deposition not will cause the volume deformation of negative electrode material, be effectively reduced
Actual current density, and then the phenomenon that reduce battery polarization.
2, the present invention provides a kind of lithium-dissimilar metal composite negative pole material preparation method, method simple possible, costs
It is low, the lithium being prepared-dissimilar metal composite negative pole material be applied to lithium battery in can effectively improve battery coulombic efficiency and
Cycle life.
3, when the lithium that the method for the present invention obtains-dissimilar metal composite negative pole material is applied to lithium secondary battery, positive electrode
Conventional anode material for lithium-ion batteries, organic positive electrode, sulphur positive electrode, air/oxygen positive electrode etc. can be used, be not necessarily to
Additionally prepare special positive electrode.
4, when the lithium that the method for the present invention obtains-dissimilar metal composite negative pole material is applied to lithium battery, can effectively inhibit
The growth of Li dendrite.By taking lithium calcium alloy negative electrode material as an example, there is CaLi inside lithium calcium alloy negative electrode material2Conductive network knot
Structure, in the discharge process of battery, the lithium metal inside lithium calcium alloy cathode dissolves consumption, exposes lithium calcium alloy CaLi2It is conductive
Network structure；And during battery charging, positive electrode takes off lithium, lithium electroplating deposition in negative electrode material, and lithium calcium alloy is born
Extremely internal CaLi2The conducting three-dimensional collector that conductive network structure can be deposited as lithium platingactive, is effectively reduced actual electricity
Current density, it is suppressed that the growth (speed of growth of Li dendrite is directly proportional to current density) of Li dendrite, and lithium platingactive is deposited on
Lithium calcium alloy CaLi2Conductive network inside configuration further limits Li dendrite, lithium calcium alloy CaLi2Conductive network is lithium deposition
Enough spaces are provided, the variation of battery volume in lithium metal deposition and course of dissolution is also inhibited.
Detailed description of the invention
Fig. 1 is the lithium calcium alloy CaLi that embodiment 3 obtains5Scanning electron microscope (SEM) figure；Wherein, (a) is lithium calcium
Alloy CaLi5The SEM on surface (b) is lithium calcium alloy CaLi5The SEM in section；
Fig. 2 is the lithium calcium alloy CaLi that embodiment 2 obtains10Scanning electron microscope (SEM) figure；Wherein, (a) is lithium calcium
Alloy CaLi10The SEM on surface (b) is lithium calcium alloy CaLi10The SEM in section；
Fig. 3 is the lithium calcium alloy CaLi that embodiment 1 obtains50Scanning electron microscope (SEM) figure；Wherein, (a) is lithium calcium
Alloy CaLi50The SEM on surface (b) is lithium calcium alloy CaLi50The SEM in section；
Fig. 4 is the lithium calcium alloy CaLi that embodiment 2 obtains10Scanning electron microscope (SEM) after electrochemistry removes lithium
Figure；Wherein, (a) is the SEM on surface, (b) is the SEM in section；
Fig. 5 is the lithium calcium alloy CaLi that embodiment 2 obtains10X-ray diffraction (XRD) map；
Fig. 6 is the ZnLi that embodiment 7 obtains10The SEM photograph on surface；
Fig. 7 is the ZnLi that embodiment 5 obtains100The SEM photograph on surface；
Fig. 8 is the ZnLi that embodiment 7 obtains10The SEM photograph on the surface after electrochemistry removes lithium；
Fig. 9 is the ZnLi that embodiment 6 obtains40The SEM photograph on the surface after electrochemistry removes lithium；
Figure 10 is the ZnLi that embodiment 5 obtains100The SEM photograph on the surface after electrochemistry removes lithium；
Figure 11 is the ZnLi that embodiment 7 obtains10X-ray diffraction (XRD) map；
Figure 12 is the lithium calcium alloy (CaLi obtained using copper foil (Bare Cu) and embodiment 210) assembling Li-Cu battery,
It is 1mA/cm in current density2Under circulating battery efficiency chart；
Figure 13 is the lithium calcium alloy (CaLi obtained using lithium foil (Bare Li) and embodiment 210) assembling Li-Li battery,
It is 1mA/cm in current density2Under charging and discharging curve figure；
Figure 14 is the lithium calcium alloy (CaLi obtained using lithium foil (Bare Li) and embodiment 210) assembling LCO battery,
Charge-discharge magnification is the charging and discharging curve figure under 1C；
Figure 15 is the ZnLi that embodiment 7 obtains10The Li-Li battery of assembling is 1mA/cm in current density2Under charge and discharge
Curve graph.
Specific embodiment
With reference to the accompanying drawings and examples, technical solution of the present invention is described in detail.
Embodiment 1
A kind of preparation method of lithium-dissimilar metal composite negative pole material, specifically includes the following steps:
Lithium metal is placed on stainless steel foil by step 1, is placed on warm table, and warm table is then heated to 200 DEG C,
Lithium metal is set to become molten condition；
Dissimilar metal calcium (Ca) is added in the lithium metal for the molten condition that step 1 obtains step 2, keeps the temperature 10min, mixes
It closes uniformly, forms the alloy of melting；Wherein, the molar ratio of dissimilar metal calcium (Ca) and lithium metal is 1:50；
Step 3, the molten alloy for obtaining step 2 are cooled to room temperature within 1min, and lithium calcium alloy CaLi can be obtained50
Negative electrode material.
Embodiment 2
A kind of preparation method of lithium-dissimilar metal composite negative pole material, specifically includes the following steps:
Step 1, by heating lithium metal to 300 DEG C, make lithium metal become molten condition；
Dissimilar metal calcium (Ca) is added in the lithium metal for the molten condition that step 1 obtains step 2, keeps the temperature 30min, mixes
It closes uniformly, forms the alloy of melting；Wherein, the molar ratio of dissimilar metal calcium (Ca) and lithium metal is 1:10；
Step 3, the molten alloy for obtaining step 2 are cooled to room temperature within 6min, and lithium calcium alloy CaLi can be obtained10
Negative electrode material.
Embodiment 3
A kind of preparation method of lithium-dissimilar metal composite negative pole material, specifically includes the following steps:
Step 1, by heating lithium metal to 500 DEG C, make lithium metal become molten condition；
Dissimilar metal calcium (Ca) is added in the lithium metal for the molten condition that step 1 obtains step 2, keeps the temperature 10min, mixes
It closes uniformly, forms the alloy of melting；Wherein, the molar ratio of dissimilar metal calcium (Ca) and lithium metal is 1:5；
Step 3, the molten alloy for obtaining step 2 are cooled to room temperature within 8min, and lithium calcium alloy CaLi can be obtained5
Negative electrode material.
Embodiment 4
A kind of preparation method of lithium-dissimilar metal composite negative pole material, specifically includes the following steps:
Step 1, by heating lithium metal to 600 DEG C, make lithium metal become molten condition；
Dissimilar metal calcium (Ca) is added in the lithium metal for the molten condition that step 1 obtains step 2, keeps the temperature 50min, mixes
It closes uniformly, forms the alloy of melting；Wherein, the molar ratio of dissimilar metal calcium (Ca) and lithium metal is 1:2；
Step 3, the molten alloy for obtaining step 2 are cooled to room temperature within 8min, and lithium calcium alloy CaLi can be obtained2
Negative electrode material.
Embodiment 5
A kind of preparation method of lithium-dissimilar metal composite negative pole material, specifically includes the following steps:
Step 1, by heating lithium metal to 800 DEG C, make lithium metal become molten condition；
Dissimilar metal zinc (Zn) is added in the lithium metal for the molten condition that step 1 obtains step 2, keeps the temperature 5min, mixing
Uniformly, the alloy of melting is formed；Wherein, the molar ratio of dissimilar metal zinc (Zn) and lithium metal is 1:100；
Step 3, the molten alloy for obtaining step 2 are cooled to room temperature within 5min, and ZnLi can be obtained100Cathode material
Material.
Embodiment 6
A kind of preparation method of lithium-dissimilar metal composite negative pole material, specifically includes the following steps:
Step 1, by heating lithium metal to 400 DEG C, make lithium metal become molten condition；
Dissimilar metal zinc (Zn) is added in the lithium metal for the molten condition that step 1 obtains step 2, keeps the temperature 20min, mixes
It closes uniformly, forms the alloy of melting；Wherein, the molar ratio of dissimilar metal zinc (Zn) and lithium metal is 1:40；
Step 3, the molten alloy for obtaining step 2 are cooled to room temperature within 3min, and ZnLi can be obtained40Cathode material
Material.
Embodiment 7
A kind of preparation method of lithium-dissimilar metal composite negative pole material, specifically includes the following steps:
Step 1, by heating lithium metal to 500 DEG C, make lithium metal become molten condition；
Dissimilar metal zinc (Zn) is added in the lithium metal for the molten condition that step 1 obtains step 2, keeps the temperature 10min, mixes
It closes uniformly, forms the alloy of melting；Wherein, the molar ratio of dissimilar metal zinc (Zn) and lithium metal is 1:10；
Step 3, the molten alloy for obtaining step 2 are cooled to room temperature within 5min, and ZnLi can be obtained10Cathode material
Material.
Embodiment 8
A kind of preparation method of lithium-dissimilar metal composite negative pole material, specifically includes the following steps:
Step 1, by heating lithium metal to 500 DEG C, make lithium metal become molten condition；
Dissimilar metal magnesium (Mg) is added in the lithium metal for the molten condition that step 1 obtains step 2, keeps the temperature 10min, mixes
It closes uniformly, forms the alloy of melting；Wherein, the molar ratio of dissimilar metal magnesium (Mg) and lithium metal is 1:10；
Step 3, the molten alloy for obtaining step 2 are cooled to room temperature within 5min, and MgLi can be obtained10Cathode material
Material.
Embodiment 9
A kind of preparation method of lithium-dissimilar metal composite negative pole material, specifically includes the following steps:
Step 1, by heating lithium metal to 500 DEG C, make lithium metal become molten condition；
Dissimilar metal indium (In) is added in the lithium metal for the molten condition that step 1 obtains step 2, keeps the temperature 10min, mixes
It closes uniformly, forms the alloy of melting；Wherein, the molar ratio of dissimilar metal indium (In) and lithium metal is 1:100；
Step 3, the molten alloy for obtaining step 2 are cooled to room temperature within 5min, and InLi can be obtained100Cathode material
Material.
Embodiment 10
A kind of preparation method of lithium-dissimilar metal composite negative pole material, specifically includes the following steps:
Step 1, by heating lithium metal to 600 DEG C, make lithium metal become molten condition；
Dissimilar metal tin (Sn) is added in the lithium metal for the molten condition that step 1 obtains step 2, keeps the temperature 8min, mixing
Uniformly, the alloy of melting is formed；Wherein, the molar ratio of dissimilar metal tin (Sn) and lithium metal is 1:20；
Step 3, the molten alloy for obtaining step 2 are cooled to room temperature within 5min, and SnLi can be obtained20Cathode material
Material.
Embodiment 11
A kind of preparation method of lithium-dissimilar metal composite negative pole material, specifically includes the following steps:
Step 1, by heating lithium metal to 600 DEG C, make lithium metal become molten condition；
Dissimilar metal strontium (Sr) is added in the lithium metal for the molten condition that step 1 obtains step 2, keeps the temperature 20min, mixes
It closes uniformly, forms the alloy of melting；Wherein, the molar ratio of dissimilar metal strontium (Sr) and lithium metal is 1:60；
Step 3, the molten alloy for obtaining step 2 are cooled to room temperature within 5min, and SrLi can be obtained60Cathode material
Material.
Embodiment 12
A kind of preparation method of lithium-dissimilar metal composite negative pole material, specifically includes the following steps:
Step 1, by heating lithium metal to 400 DEG C, make lithium metal become molten condition；
Dissimilar metal antimony (Sb) is added in the lithium metal for the molten condition that step 1 obtains step 2, keeps the temperature 20min, mixes
It closes uniformly, forms the alloy of melting；Wherein, the molar ratio of dissimilar metal antimony (Sb) and lithium metal is 1:80；
Step 3, the molten alloy for obtaining step 2 are cooled to room temperature within 5min, and SbLi can be obtained80Cathode material
Material.
Embodiment 13
A kind of preparation method of lithium-dissimilar metal composite negative pole material, specifically includes the following steps:
Step 1, by heating lithium metal to 500 DEG C, make lithium metal become molten condition；
Dissimilar metal barium (Ba) is added in the lithium metal for the molten condition that step 1 obtains step 2, keeps the temperature 10min, mixes
It closes uniformly, forms the alloy of melting；Wherein, the molar ratio of dissimilar metal barium (Ba) and lithium metal is 1:100；
Step 3, the molten alloy for obtaining step 2 are cooled to room temperature within 5min, and BaLi can be obtained100Cathode material
Material.
Embodiment 14
A kind of preparation method of lithium-dissimilar metal composite negative pole material, specifically includes the following steps:
Step 1, by heating lithium metal to 500 DEG C, make lithium metal become molten condition；
Dissimilar metal lead (Pb) is added in the lithium metal for the molten condition that step 1 obtains step 2, keeps the temperature 10min, mixes
It closes uniformly, forms the alloy of melting；Wherein, the molar ratio of dissimilar metal lead (Pb) and lithium metal is 1:30；
Step 3, the molten alloy for obtaining step 2 are cooled to room temperature within 5min, and PbLi can be obtained30Cathode material
Material.
Embodiment 15
A kind of preparation method of lithium-dissimilar metal composite negative pole material, specifically includes the following steps:
Step 1, by heating lithium metal to 500 DEG C, make lithium metal become molten condition；
Dissimilar metal bismuth (Bi) is added in the lithium metal for the molten condition that step 1 obtains step 2, keeps the temperature 10min, mixes
It closes uniformly, forms the alloy of melting；Wherein, the molar ratio of dissimilar metal bismuth (Bi) and lithium metal is 1:50；
Step 3, the molten alloy for obtaining step 2 are cooled to room temperature within 5min, and BiLi can be obtained50Cathode material
Material.
Embodiment 16
A kind of preparation method of lithium-dissimilar metal composite negative pole material, specifically includes the following steps:
Step 1, by heating lithium metal to 500 DEG C, make lithium metal become molten condition；
Dissimilar metal silicon (Si) is added in the lithium metal for the molten condition that step 1 obtains step 2, keeps the temperature 10min, mixes
It closes uniformly, forms the alloy of melting；Wherein, the molar ratio of dissimilar metal silicon (Si) and lithium metal is 1:10；
Step 3, the molten alloy for obtaining step 2 are cooled to room temperature within 5min, and SiLi can be obtained10Cathode material
Material.
Embodiment 17
A kind of preparation method of lithium-dissimilar metal composite negative pole material, specifically includes the following steps:
Step 1, by heating lithium metal to 400 DEG C, make lithium metal become molten condition；
Step 2 dissimilar metal calcium (Ca) and zinc (Zn) is added in the lithium metal for the molten condition that step 1 obtains, heat preservation
10min is uniformly mixed, forms the alloy of melting；Wherein, the molar ratio (n of dissimilar metal calcium (Ca) zinc (Zn) and lithium metalCa+
nZn): nLi=1:20；
Step 3, the molten alloy for obtaining step 2 are cooled to room temperature within 5min, and CaZnLi can be obtained40Cathode material
Material.
Embodiment 18
A kind of preparation method of lithium-dissimilar metal composite negative pole material, specifically includes the following steps:
Step 1, by heating lithium metal to 600 DEG C, make lithium metal become molten condition；
Step 2 dissimilar metal magnesium (Mg) and aluminium (Al) is added in the lithium metal for the molten condition that step 1 obtains, heat preservation
30min is uniformly mixed, forms the alloy of melting；Wherein, the molar ratio (n of dissimilar metal magnesium (Mg) aluminium (Al) and lithium metalMg+
nAl): nLi=1:10；
Step 3, the molten alloy for obtaining step 2 are cooled to room temperature within 6min, and MgAlLi can be obtained20Cathode material
Material.
Embodiment 19
A kind of preparation method of lithium-dissimilar metal composite negative pole material, specifically includes the following steps:
Step 1, by heating lithium metal to 500 DEG C, make lithium metal become molten condition；
Step 2 dissimilar metal barium (Ba) and strontium (Sr) is added in the lithium metal for the molten condition that step 1 obtains, heat preservation
10min is uniformly mixed, forms the alloy of melting；Wherein, the molar ratio (n of dissimilar metal barium (Ba) strontium (Sr) and lithium metalBa+
nSr): nLi=1:50；
Step 3, the molten alloy for obtaining step 2 are cooled to room temperature within 5min, and BaSrLi can be obtained100Cathode
Material.
Embodiment 20
A kind of preparation method of lithium-dissimilar metal composite negative pole material, specifically includes the following steps:
Step 1, by heating lithium metal to 500 DEG C, make lithium metal become molten condition；
The lithium metal of step 2, the molten condition for obtaining dissimilar metal lead (Pb), barium (Ba) and silicon (Si) addition step 1
In, 10min is kept the temperature, is uniformly mixed, forms the alloy of melting；Mole of dissimilar metal lead (Pb) barium (Ba) silicon (Si) and lithium metal
Than (nBa+nSi+nPb): nLi=1:40；
Step 3, the molten alloy for obtaining step 2 are cooled to room temperature within 5min, and PbBaSiLi can be obtained120It is negative
Pole material.
The lithium calcium alloy that the embodiment of the present invention is prepared carries out morphology analysis, as a result picture 1-4.By Fig. 1-4 it is found that
The content of calcium is more in lithium calcium alloy, lithium calcium alloy CaLi2Network structure content is more, and will appear biggish lithium calcium alloy
Particle；When calcium content reduces, lithium calcium alloy content is reduced, CaLi2Network structure is also increasingly thinner, shows the content of calcium to lithium
Calcium alloy CaLi2Crystal shape has important influence.When the atom number ratio of calcium and lithium is 1:10, i.e. CaLi10When, obtained lithium
CaLi in calcium alloy2Network structure is more dispersed, even, shape is more regular.
Fig. 4 is the lithium calcium alloy CaLi that embodiment 2 obtains10Scanning electron microscope (SEM) after electrochemistry removes lithium
Figure；As shown in Figure 4, calcium metal network structure is dispersed in inside lithium calcium alloy combination electrode as skeleton structure.
Fig. 5 is the lithium calcium alloy CaLi that embodiment 2 obtains10X-ray diffraction (XRD) map；As shown in Figure 5, embodiment 2
Obtained lithium calcium alloy CaLi10XRD spectrum show lithium simple substance and lithium calcium alloy CaLi2Characteristic diffraction peak.
The lithium calcium alloy CaLi that embodiment 2 is obtained10Calcium metal skeleton structure after electrochemistry removes lithium is applied to Li-
In Cu battery system, in anhydrous and oxygen-free and it is full of assembling Li-Cu battery in the glove box of argon gas.Detailed process are as follows: use 1mol/
L LiTFSI+2%LiNO3Be dissolved in DOL:DME=1:1 electrolyte system, using diameter for 8mm metallic lithium foil as cathode, directly
The Celgard 2325 that diameter is 19mm is used as diaphragm, and the copper foil of calcium skeleton structure or routine that diameter is 15mm is used as to electrode,
It is packaged in CR2032 button cell, carries out constant current charge-discharge test, current density 1mA/cm2, discharge time 1h, then
1V is charged to, it is as shown in figure 12 to obtain circulating battery efficiency chart.As shown in Figure 12, it is used as using conventional copper foil to electrode assembling
Battery, coulombic efficiency is lower, and cycle life is shorter；And the lithium calcium alloy CaLi obtained using embodiment 210It is removed through electrochemistry
As the battery to electrode assembling, coulombic efficiency greatly promotes calcium metal skeleton structure after removing lithium, close to 100%, recycles
Service life greatly promotes, and electrochemical impedance is smaller.
The lithium calcium alloy CaLi that embodiment 2 is obtained10Negative electrode material is applied in Li-Li battery system, in anhydrous and oxygen-free
And Li-Li battery is assembled in the glove box full of argon gas.Detailed process are as follows: use 1mol/LLiTFSI+2%LiNO3It is dissolved in
DOL:DME=1:1 electrolyte system is the lithium calcium alloy CaLi of 15mm with diameter10As working electrode, diameter is 19mm's
Celgard 2325 is used as diaphragm, and diameter is the lithium calcium alloy CaLi of 15mm10Or lithium foil is used as to electrode, is packaged in CR2032 button
In formula battery, constant current charge-discharge test, current density 1mA/cm are carried out2, the charge and discharge time is respectively 1h, and obtained charge and discharge are bent
Line is as shown in figure 13.As shown in Figure 13, cause to polarize since Charge-transfer resistance is larger using the battery of lithium foil assembling larger, and
And as the increase of circulation time, battery polarization are more and more obvious, show that lithium metal constantly consumes electrolyte in cyclic process,
Impedance persistently increases, and eventually forms Li dendrite across diaphragm and causes internal short-circuit；And the lithium calcium alloy obtained using embodiment 2
CaLi10The battery polarization of assembling is smaller, and with the increase of circulation time, battery polarization increase is smaller, shows that embodiment 2 obtains
The lithium calcium alloy CaLi arrived10Charge-transfer resistance it is smaller, can effectively inhibit reacting for lithium metal and electrolyte, cycle life
Also it mentions, reaches 1000 times or more significantly.
The lithium calcium alloy CaLi that embodiment 2 is obtained10Negative electrode material is applied in lithium-cobalt acid lithium (LCO) battery system,
Anhydrous and oxygen-free and full of argon gas glove box in assemble lithium-cobalt acid lithium battery.Detailed process are as follows: use 1mol/L LiPF6It is dissolved in
EC:DEC:DMC=1:1:1 electrolyte system is the lithium calcium alloy CaLi of 15mm with diameter10As cathode, diameter is 19mm's
Celgard 2325 is used as diaphragm, and the cobalt acid lithium electrode slice that diameter is 10mm is packaged in CR2032 button cell as anode,
Constant current charge-discharge test under 1C multiplying power is carried out, as a result as shown in figure 14.As shown in Figure 14, using lithium calcium alloy CaLi10Assembling
Compared with the battery that lithium foil assembles, discharge capacity and capacity retention ratio all have a distinct increment battery.
The ZnLi that embodiment 7 is obtained10Negative electrode material is applied in lithium-lithium battery system, in anhydrous and oxygen-free and it is full of argon
Li-Li battery is assembled in the glove box of gas.Detailed process are as follows: use 1mol/L LiPF6It is dissolved in EC:DEC=1:1 electrolyte
System, is the lithium-zinc alloy ZnLi of 15mm with diameter10As working electrode, the Celgard 2325 that diameter is 19mm is used as diaphragm,
Diameter is the lithium-zinc alloy ZnLi of 15mm10It as to electrode, is packaged in CR2032 button cell, carries out constant current charge-discharge survey
Examination, current density 1mA/cm2, the charge and discharge time is respectively 1h, and obtained charging and discharging curve is as shown in figure 15.As shown in Figure 15,
The ZnLi obtained using the embodiment of the present invention 710The polarization of the battery of assembling is smaller, and with the increase battery pole of circulation time
It is smaller to change increase, shows the ZnLi that embodiment 7 obtains10Charge-transfer resistance it is smaller, can effectively inhibit lithium metal and electrolysis
The reaction of liquid, cycle life are also mentioned significantly, reach 400h or more.
Claims (5)
1. a kind of lithium-dissimilar metal composite negative pole material, including lithium simple substance phase and lithium-dissimilar metal alloy phase two phase structure,
In, the molar ratio of lithium and dissimilar metal is (1~100): 1.
2. a kind of lithium-dissimilar metal composite negative pole material preparation method, which comprises the following steps:
Step 1, by heating lithium metal to 200~800 DEG C, make lithium metal become molten condition；
Dissimilar metal is added in the lithium metal for the molten condition that step 1 obtains step 2, keeps the temperature 5~60min, is uniformly mixed,
Form the alloy of melting；Wherein, the dissimilar metal be magnesium, calcium, zinc, indium, aluminium, tin, silicon, strontium, antimony, barium, lead, in bismuth at least
It is a kind of；
Step 3, the molten alloy for obtaining step 2 are cooled to room temperature, and the lithium-dissimilar metal composite negative pole material can be obtained
Material.
3. lithium according to claim 2-dissimilar metal composite negative pole material preparation method, which is characterized in that step 2 institute
The molar ratio for stating lithium metal described in dissimilar metal and step 1 is 1:(1~100).
4. lithium according to claim 2-dissimilar metal composite negative pole material preparation method, which is characterized in that in step 3
The time that molten alloy is cooled to room temperature is 1~10min.
5. lithium described in any one of claims 1 to 4-application of the dissimilar metal composite negative pole material in lithium battery.
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Application publication date: 20190618 |