CN106784666B - The preparation method of carbon-coated nano boron lithium composite material for lithium-sulfur cell cathode - Google Patents
The preparation method of carbon-coated nano boron lithium composite material for lithium-sulfur cell cathode Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 85
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 72
- PPTSBERGOGHCHC-UHFFFAOYSA-N boron lithium Chemical compound [Li].[B] PPTSBERGOGHCHC-UHFFFAOYSA-N 0.000 title claims abstract description 63
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 239000002131 composite material Substances 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 61
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 55
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000004202 carbamide Substances 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims abstract description 14
- 239000008103 glucose Substances 0.000 claims abstract description 14
- HZRMTWQRDMYLNW-UHFFFAOYSA-N lithium metaborate Chemical compound [Li+].[O-]B=O HZRMTWQRDMYLNW-UHFFFAOYSA-N 0.000 claims abstract description 13
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 12
- 239000008367 deionised water Substances 0.000 claims abstract description 11
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 11
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims abstract description 9
- 238000010792 warming Methods 0.000 claims abstract description 9
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 7
- 238000004090 dissolution Methods 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 15
- 235000010489 acacia gum Nutrition 0.000 claims description 10
- 239000001785 acacia senegal l. willd gum Substances 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 7
- 239000006230 acetylene black Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 229920000084 Gum arabic Polymers 0.000 claims description 5
- 238000000748 compression moulding Methods 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- 238000003763 carbonization Methods 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 4
- 230000005611 electricity Effects 0.000 claims description 3
- GZCGUPFRVQAUEE-VANKVMQKSA-N aldehydo-L-glucose Chemical compound OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)C=O GZCGUPFRVQAUEE-VANKVMQKSA-N 0.000 claims description 2
- 238000009790 rate-determining step (RDS) Methods 0.000 claims description 2
- 210000002700 urine Anatomy 0.000 claims 1
- 239000003643 water by type Substances 0.000 claims 1
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 24
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 21
- 239000007773 negative electrode material Substances 0.000 abstract description 16
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 238000007599 discharging Methods 0.000 abstract description 5
- 238000005516 engineering process Methods 0.000 abstract description 4
- 210000004027 cell Anatomy 0.000 description 32
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 26
- 229910052717 sulfur Inorganic materials 0.000 description 19
- 239000011593 sulfur Substances 0.000 description 19
- 239000000243 solution Substances 0.000 description 17
- 238000006243 chemical reaction Methods 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 10
- 239000003792 electrolyte Substances 0.000 description 9
- 229910002804 graphite Inorganic materials 0.000 description 9
- 239000010439 graphite Substances 0.000 description 9
- 229910000733 Li alloy Inorganic materials 0.000 description 8
- 239000001989 lithium alloy Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 239000005077 polysulfide Substances 0.000 description 7
- 229920001021 polysulfide Polymers 0.000 description 7
- 150000008117 polysulfides Polymers 0.000 description 7
- 239000011230 binding agent Substances 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 6
- 238000001694 spray drying Methods 0.000 description 6
- 229930006000 Sucrose Natural products 0.000 description 5
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000005720 sucrose Substances 0.000 description 5
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 4
- 229910013458 LiC6 Inorganic materials 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 239000005864 Sulphur Substances 0.000 description 4
- 150000004862 dioxolanes Chemical class 0.000 description 4
- 238000003780 insertion Methods 0.000 description 4
- 230000037431 insertion Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 238000003805 vibration mixing Methods 0.000 description 4
- 239000004411 aluminium Substances 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000005253 cladding Methods 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000009831 deintercalation Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- GLNWILHOFOBOFD-UHFFFAOYSA-N lithium sulfide Chemical compound [Li+].[Li+].[S-2] GLNWILHOFOBOFD-UHFFFAOYSA-N 0.000 description 3
- -1 resourceful Chemical compound 0.000 description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229910001216 Li2S Inorganic materials 0.000 description 2
- 229910010676 Li5B4 Inorganic materials 0.000 description 2
- 229910013178 LiBO2 Inorganic materials 0.000 description 2
- 229910032387 LiCoO2 Inorganic materials 0.000 description 2
- 229910018688 LixC6 Inorganic materials 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Substances [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 230000001473 noxious effect Effects 0.000 description 2
- 238000002161 passivation Methods 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- VJRLOPVXROQXLO-BTVCFUMJSA-N (2r,3s,4r,5r)-2,3,4,5,6-pentahydroxyhexanal;urea Chemical compound NC(N)=O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O VJRLOPVXROQXLO-BTVCFUMJSA-N 0.000 description 1
- 229910000619 316 stainless steel Inorganic materials 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910020042 NbS2 Inorganic materials 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N SnO2 Inorganic materials O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910003092 TiS2 Inorganic materials 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 230000022131 cell cycle Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 238000006392 deoxygenation reaction Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 150000002642 lithium compounds Chemical class 0.000 description 1
- 239000000320 mechanical mixture Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- VGTPKLINSHNZRD-UHFFFAOYSA-N oxoborinic acid Chemical compound OB=O VGTPKLINSHNZRD-UHFFFAOYSA-N 0.000 description 1
- 239000002006 petroleum coke Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 210000000952 spleen Anatomy 0.000 description 1
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Classifications
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1397—Processes of manufacture of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Composite Materials (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
The present invention relates to lithium ion battery technologies, it is desirable to provide a kind of preparation method of the carbon-coated nano boron lithium composite material for lithium-sulfur cell cathode.It include: that glucose, urea and lithium metaborate are added in deionized water, ultrasonic vibration mixed dissolution；After solution is spray-dried, solidify 6 hours formation presomas at 106 DEG C；It is warming up to 500 DEG C under nitrogen atmosphere protection, after constant temperature is carbonized 2 hours, is heated 2~10 hours at 900~1300 DEG C, obtains carbon-coated nano boron lithium composite material.The lithium-sulfur cell formed using carbon-coated nano boron lithium as negative electrode material in the present invention, battery core can produce in dry air, greatly improve the security and reliability and production efficiency of lithium-sulfur cell production, reduce equipment cost and production cost.The charge and discharge cycles stability of boron lithium electrode can be greatlyd improve, the high power charging-discharging cycle life of lithium sulphion battery is improved.
Description
Technical field
The present invention relates to a kind of lithium ion battery technologies, and more specifically, the invention relates to using for lithium-sulfur cell cathode
The preparation method of carbon-coated nano boron lithium composite material.
Background technique
Lithium ion battery has many advantages, such as that light-weight, capacity is big, memory-less effect, thus has obtained commonly used.Now
Many digital equipments all use lithium ion battery and make power supply.The energy density of lithium ion battery is very high, its capacity is same
1.5~2 times of the nickel-metal hydride battery of weight, and have many advantages, such as very low self-discharge rate, be that it is answered extensively without noxious material
Major reason.Nineteen ninety Japan Nagoura et al. is developed into using petroleum coke as cathode, with LiCoO2For the lithium ion of anode
Battery: LiC6|LiClO4-PC+EC|LiCoO2.The same year.Moli and two big battery company of sony, which declare to release with graphitic carbon, is
The lithium ion battery of cathode.1991, Sony energy technology company and battery unit developed jointly one kind with glycan alcohol heat
Solve the lithium ion battery that carbon (PFA) is cathode.Lithium ion battery tradition negative electrode material has graphite (C6), sulfide: TiS2、NbS2,
Oxide: WO3、V2O5、SnO2Deng.By taking graphite cathode material as an example, negative reaction in charge and discharge process:
C6+xLi++ xe==LixC6
When charging the battery, there is lithium ion generation on the anode of battery, the lithium ion of generation is transported by electrolyte
Move cathode.And be in layer structure as the graphite of cathode, the lithium ion for reaching cathode is just embedded into graphite layers, forms embedding lithium
Compound (LixC6), the lithium ion of insertion is more, and charging capacity is higher.When discharging battery, in graphite linings
Lithium ion abjection, and move back into anode.The lithium ion that anode can be returned to is more, and discharge capacity is higher.
Negative electrode material as lithium battery must be have it is claimed below: (1) lithium storage capacity is high；(2) lithium is in negative electrode material
In insertion, deintercalation reaction it is fast, i.e. diffusion coefficient of the lithium ion in solid phase is big, in the mobile impedance of electrode-electrolyte interface
It is small；(3) existence of the lithium ion in electrode material is stablized；(4) in the charge and discharge cycles of battery, negative electrode material volume becomes
Change small；(5) electron conduction is high；(6) negative electrode material does not dissolve in the electrolytic solution.
The selection of negative electrode material has a great impact to the performance of battery.Cathode of lithium battery research and development at present is main
Concentrate on carbon material and the metal oxide with special construction.The most commonly used is graphite electrodes, because graphitic conductive is good, knot
Brilliant degree is higher, has good layer structure, is suitble to the insertion and deintercalation of lithium.And its intercalation potential is low and flat, can be
Lithium ion battery provides high stable operating voltage are as follows: (vs.Li between 0.00~0.20V+/ Li), the theoretical embedding lithium of graphite holds
Amount is 372mAh/g, LiC6Theory take off lithium capacity be 340mAh/g.
The embedding lithium specific capacity of graphite negative electrodes material is about 330~350mAh/g at present, is unable to satisfy people to high capacity
The demand of electrode.Boron lithium alloy can reversible removal lithium embedded, wherein Li5B4Theory take off lithium capacity be up to 1700mAh/g, be LiC6
5 times of the de- lithium capacity of theory.The embedding lithium capacity of theory of boron is up to 3100mAh/g, and 8.3 times of the theoretical embedding lithium capacity of graphite.Boron lithium
Alloy provides lithium source as negative electrode active material, for lithium-sulfur cell, is a kind of lithium cell cathode material of great potential.
Lithium-sulfur cell is using lithium metal as negative electrode material, and using liquid electrolyte, negative reaction is that lithium loses electronics when electric discharge
Become lithium ion, it is that sulphur and lithium ion and electron reaction generate sulfide that anode, which reacts, and the potential difference of anode and negative reaction is
For discharge voltage provided by lithium-sulfur cell.Under applied voltage effect, the anode and negative reaction of lithium-sulfur cell are inversely carried out,
As charging process.Become S completely according to the elemental sulfur of unit mass2-The electricity that can be provided can obtain the theoretical discharge matter of sulphur
Amount specific capacity is 1675mAh g-1, micro-pore septum separates sulphur anode and lithium anode to form traditional lithium-sulfur cell.
The charging and discharging reaction of sulfur electrode is more complex, and discharge process mainly includes two steps, respectively corresponds two
Discharge platform: (1) corresponding S8Cyclic structure become Sn 2-The chain structure of (3≤n≤7) ion, and and Li+In conjunction with generation polysulfide
Change lithium (Li2Sn), discharge platform of the reaction on discharge curve near corresponding 2.4~2.1V；(2) corresponding Sn 2-The chain of ion
Structure becomes S2-And S2 2-And and Li+In conjunction with generation Li2S2And Li2S, the reaction correspond in discharge curve 2.1~1.8V nearby compared with
Long discharge platform, the platform are the main discharge regions of lithium-sulfur cell.It is located at 2.5~2.05V potential region pair upon discharging
It answers elemental sulfur reduction to generate the further reduction of soluble polysulfide and polysulfide, is located at 2.05~1.5V potential region pair
Soluble polysulfide reduction is answered to generate lithium sulfide solid film, it is covered on conductive carbon matrix surface.When charging, in sulfur electrode
Li2S and Li2S2It is oxidized S8And Sm 2-(6≤m≤7) can not be completely oxidized to S8, charging reaction correspondence in charging curve
Charging platform near 2.5~2.4V.The problem of lithium-sulfur cell maximum is at present: being formed in charge and discharge process and is dissolved in electrolyte
Poly- lithium sulfide, the poly- lithium sulfide of dissolution reacts with negative metal lithium, causes capacitance loss, lithium-sulfur cell capacity is caused quickly to decline
It moves back, shows very poor cycle life.Polysulfide ion can significantly improve lithium sulphur with reacting for lithium metal in inhibition lithium-sulfur cell
The cycle life of battery.
Summary of the invention
The technical problem to be solved by the present invention is to overcome deficiency in the prior art, provide a kind of negative for lithium-sulfur cell
The preparation method of the carbon-coated nano boron lithium composite material of pole.
In order to solve the technical problem, solution of the invention are as follows:
A kind of preparation method of carbon-coated nano boron lithium composite material for lithium-sulfur cell cathode, including following step are provided
It is rapid:
(1) glucose, urea and lithium metaborate are added in deionized water, ultrasonic vibration mixes 30 minutes, makes metaboric acid
Lithium, urea and glucose dissolution；After solution is spray-dried, solidify 6 hours formation presomas at 106 DEG C；
The mass ratio of glucose, urea and lithium metaborate is that 6: 1: 1~3,1g urea corresponds to 100mL deionized water；
(2) presoma is warming up to 500 DEG C under nitrogen atmosphere protection, after constant temperature is carbonized 2 hours, at 900~1300 DEG C
Lower heating 2~10 hours, obtains carbon-coated nano boron lithium composite material.
In the present invention, the heating rate in rate-determining steps (2) is 10 DEG C/min.
Invention further provides the sides that lithium battery cathode plate is prepared using aforementioned carbon-coated nano boron lithium composite material
Method, comprising the following steps:
(1) in mass ratio 95: 5 NMP (N-Methyl pyrrolidone) and gummi arabicum pulveratum are weighed；Gummi arabicum pulveratum is added
In NMP, 90 DEG C are heated under stirring；Continue stirring 2 hours, obtains the nmp solution of Arabic gum, be cooled to room temperature spare；
(2) in mass ratio 85: 10: 100 to weigh carbon-coated nano boron lithium composite material, acetylene black and Arabic gum NMP molten
Liquid is modulated into paste after mixed grinding, is coated on copper film；In 100Kg/cm after drying in the shade2Pressure under compression moulding, obtain lithium
Battery cathode sheet.
The principle of the present invention description:
Glucose, urea, lithium metaborate are dissolved in water by the present invention, are calcined after spray drying, and carbon-coated nano is formed
Boron lithium, and in this, as lithium-sulfur cell negative electrode material.Boron lithium alloy can reversible removal lithium embedded, wherein Li5B4Theory take off lithium capacity
Up to 1700mAh/g is LiC65 times of the de- lithium capacity of theory.But the volume change of negative electrode material is quite big when charge and discharge, carbon packet
It covers, the volume change of negative electrode material can be limited in carbon shell, reduce the influence to electrode structure.Carbon-coated nano boron lithium is not
Only lithium-sulfur cell provides lithium source, while also avoiding reacting for polysulfide ion and lithium metal, significantly improves lithium-sulfur cell
Cycle life.
When using boron lithium as negative electrode material, the electrochemical reaction of cathode in discharge process are as follows:
LiB==B+Li++e
In the present invention, it is spray-dried so that lithium metaborate, urea, glucose uniformly mix, water is in fast evaporation process shape
At duct, porous mixture is formed.Pre-polymerization occurs for urea and glucose, becomes binder and firmly wraps up lithium metaborate；
In the present invention, solidify 6 hours at 106 DEG C and make urea and glucose polymerisation complete, forms glucose urea resin,
The water generated during resin polymerization, evaporation form micropore；
In the present invention, it is warming up to 500 DEG C, constant temperature 2 hours, so that resin starts to be carbonized；
In the present invention, during heating 2~10 hours at 900~1300 DEG C, LiBO2It melts, by pitch shake
It vents one's spleen reduction, deoxygenation occurs, form boron lithium alloy, be covered by carbon shell, obtain carbon-coated nano boron lithium；
In the present invention, LiBO2Deoxidation forms remaining void in carbon shell, can be absorbed brought by boron lithium alloy removal lithium embedded
Volume expansion, so that it is unstable to solve electrode structure caused by boron lithium alloy removal lithium embedded to a certain extent；
With the progress of charge and discharge cycles, the rupture and disintegration of carbon shell inevitably occurs.Therefore it in the present invention, uses
Arabic gum binder flexible then can guarantee that the rupture of carbon shell and disintegration will not influence the structural stability of electrode, thus pole
The earth improves the charge and discharge cycles stability of boron lithium electrode.
Carbon coating method provided by the invention, can effectively improve the electric conductivity of boron lithium alloy, so that rate charge-discharge performance
It is significantly improved；The present invention uses cheap glucose and urea, resourceful, and carbon-coated nano boron lithium synthesis technology
Simply, noxious material is free of, is a kind of easy synthetic method for obtaining carbon-coated nano boron lithium, has the energy of large-scale production
Power.
Compared with prior art, the invention has the benefit that
1, the present invention has high removal lithium embedded specific capacity, the electric conductivity of carbon shell and carbon shell using carbon-coated nano boron lithium
Interior existing built-in space, forms a kind of high performance lithium ion battery negative material.It is provided especially for lithium-sulfur cell
Lithium source, carbon-coated nano boron lithium is stable in the air, therefore it is raw to avoid the battery that lithium-sulfur cell must be assembled in glove box lithium
The defect of production. art.Therefore, the lithium-sulfur cell formed using carbon-coated nano boron lithium as negative electrode material, battery core can be in dry skies
Produced in gas, greatly improve lithium-sulfur cell production security and reliability and production efficiency, reduce equipment cost and
Production cost.
2, negative electrode active material of the carbon-coated nano boron lithium as lithium sulphion battery in the micropore in porous carbon, is filling
Occur not form point discharge in electric process, the generation of dendrite will not be caused, reduces the volume change pair of boron lithium alloy removal lithium embedded
The influence of electrode structure avoids reacting for lithium metal and polysulfide ion.Using Arabic gum binder flexible, then can guarantee
The rupture and disintegration of carbon shell will not influence the structural stability of electrode, to greatly improve the charge and discharge cycles of boron lithium electrode
Stability.These features show especially prominent in terms of the high power charging-discharging cycle life for improving lithium sulphion battery.So far
Until the present, not using carbon-coated nano boron lithium as the report of lithium sulphion cell negative electrode material.
Detailed description of the invention
Fig. 1 is the transmission electron microscope photo of the carbon-coated nano boron lithium composite material prepared in embodiment two.
Fig. 2 is the traditional lithium sulphur prepared in embodiment seven and eight and the lithium sulphion battery using carbon-coated nano boron lithium
High rate performance.
Fig. 3 is the traditional lithium sulphur prepared in embodiment seven and eight and the lithium sulphion battery using carbon-coated nano boron lithium
1C charge-discharge performance.
Appended drawing reference in figure are as follows: 2-1-1 uses the 0.2C discharge capacity of the lithium sulphion battery of carbon-coated nano boron lithium,
2-1-2 uses the 0.5C discharge capacity of the lithium sulphion battery of carbon-coated nano boron lithium, and 2-1-3 uses carbon-coated nano boron lithium
The 1C discharge capacity of lithium sulphion battery, 2C discharge capacity of the 2-1-4 using the lithium sulphion battery of carbon-coated nano boron lithium, 2-
1-5 uses the 5C discharge capacity of the lithium sulphion battery of carbon-coated nano boron lithium, and 2-1-6 uses the lithium sulphur of carbon-coated nano boron lithium
The 10C discharge capacity of ion battery；The 0.2C discharge capacity of 2-2-1 tradition lithium sulphion battery, 2-2-2 tradition lithium sulphion electricity
The 0.5C discharge capacity in pond, the 1C discharge capacity of 2-2-3 tradition lithium sulphion battery, the 2C of 2-2-4 tradition lithium sulphion battery
Discharge capacity, the 5C discharge capacity of 2-2-5 tradition lithium sulphion battery, the 10C of 2-2-6 tradition lithium sulphion battery, which discharges, to be held
Amount；1C charge/discharge capacity decline curve of the 3-1 using the lithium sulphion battery of carbon-coated nano boron lithium, 3-2 tradition lithium sulphion
The 1C charge/discharge capacity decline curve of battery.
Specific embodiment
It present invention will be described in detail below.
Embodiment one: precursor preparation
Glucose (6g), urea (1g), lithium metaborate (1g) is taken to be added into 100mL deionized water, ultrasonic vibration mixing
30 minutes formation solution；Solidify 6 hours formation presomas after spray drying at 106 DEG C.
Embodiment two: carbon-coated nano boron lithium preparation
Glucose (6g), urea (1g), lithium metaborate (2g) is taken to be added into 100mL deionized water, ultrasonic vibration mixing
30 minutes formation solution；Solidify 6 hours formation presomas after spray drying at 106 DEG C.Presoma is protected in nitrogen atmosphere
Under be warming up to 500 DEG C and be carbonized, after carbonization 2 hours, be heated to 900 DEG C with the heating rate of 10 DEG C/min, constant temperature 10 hours,
It is cooled to room temperature and forms carbon-coated nano boron lithium composite material.
Embodiment three: binder modulation
City dealer gummi arabicum pulveratum (5g) is added in 95g NMP and is heated with stirring to 90 DEG C, stirring obtains Arabic gum in 2 hours
Nmp solution is cooled to room temperature spare.
Example IV: cathode preparation
Glucose (6g), urea (1g), lithium metaborate (3g) is taken to be added into 100mL deionized water, ultrasonic vibration mixing
30 minutes formation solution；Solidify 6 hours formation presomas after spray drying at 106 DEG C.Presoma is protected in nitrogen atmosphere
Under be warming up to 500 DEG C and be carbonized, after carbonization 2 hours, be heated to 1100 DEG C with the heating rate of 10 DEG C/min, constant temperature 6 hours,
It is cooled to room temperature and forms carbon-coated nano boron lithium composite material.
Take binder obtained in acetylene black, above-mentioned carbon-coated nano boron lithium composite material (0.85g) and embodiment three molten
Liquid (1g), by carbon-coated nano boron lithium, acetylene black, Arabic gum nmp solution 85: 10: 100 mixed grinding of mass ratio, modulation
At being coated on copper film after paste；In 100Kg cm after drying in the shade-2Pressure under compression moulding, obtain cladding nanometer boron cathode of lithium
Piece.
Embodiment five: sulfur electrode material preparation
It takes sucrose 10g to be heated to 80 DEG C to be dissolved in the dilute sulfuric acid of 10wt% (10mL), thiocarbamide 20g is heated to 40 DEG C of dissolutions
In 20mL deionized water, the molar ratio of sucrose and thiocarbamide is 1:2.Thiourea solution is added in sucrose solution, 90 DEG C of water are placed in
In bath, it is sufficiently stirred.Reaction 45 minutes after, liquid viscosity significantly increases, color from without through it is pale yellow become orange red after, be added
Polymerization is terminated in 40mL deionized water, cooling obtains sucrose thiocarbamide prepolymer solution.
1 beaker separately is taken, by Nano-meter CaCO33Powder 5g is dispersed in 30mL deionization, obtains suspension, is added to
In sucrose thiocarbamide prepolymer solution, 85 DEG C of water-bath heating, spray drying obtains macropore carbon matrix precursor after being stirred to react 50 minutes.
160 DEG C are warming up to from room temperature with the speed of 10 DEG C/min under nitrogen atmosphere, keeps the temperature 2 hours, carries out depth polymerization.So
900 DEG C are warming up to the speed of 10 DEG C/min afterwards, 2 hours is kept the temperature, is carbonized, while CaCO3It decomposes and generates CO2, formed logical
Hole takes out after cooling, black powder is obtained after ball milling, then uses the 10wt% hydrochloric acid of 50mL, 2 hours removal moulds of stir process
Plate is dried to obtain sulfur-bearing, nitrogen macropore carbon after being rinsed with deionized water.
In mass ratio it is that 7: 3 mechanical mixtures are uniform by elemental sulfur and sulfur-bearing, nitrogen macropore carbon, is placed in 316 stainless steel materials
In reactor, it is heated to 80 DEG C after then vacuumizing reactor, completes supporting for sulphur after heating 5 hours, then by reaction product
25 DEG C are cooled to, obtains sulfur-bearing, nitrogen macropore carbon carries sulfur materials.
Embodiment six: sulfur electrode preparation
Sulfur-bearing, the nitrogen macropore carbon prepared in Example five carries to be bonded obtained in sulfur materials (0.85g) and embodiment three
Agent solution (1g), sulfur-bearing, nitrogen macropore carbon carry sulfur materials, acetylene black, Arabic gum nmp solution, in mass ratio 85: 10: 100 mixing
Grinding, is coated in aluminium film after being modulated into paste；In 100Kg/cm after drying in the shade2Pressure under compression moulding, obtain lithium-sulfur cell
Positive plate.
Embodiment seven: lithium-sulfur cell preparation
Sulfur electrode obtained in embodiment six (taking diameter is the disk of 18mm) is placed in city and buys to resell button cell shell
(CR2025) in, sulfur electrode substrate aluminium film is contacted with battery case；City dealer microporous polypropylene membrane (diameter 19mm) is placed in
On sulfur electrode；Lithium piece (taking diameter is 18mm, the disk of thick 0.2mm) is placed on diaphragm；Diameter is 18mm, thickness on pad
After 1mm, the foam nickel sheet that voidage is 98%, electrolyte 0.2mL is added, is sealed after encrypting seal and battery cover, obtains button
Lithium-sulfur cell.Electrolyte is with Li [CF3SO2)2N] (LiTFSI) be solute, dioxolanes (C3H6O2) and ethylene glycol monomethyl ether
(C4H10O2) mixture be solvent, the volume ratio of dioxolanes and ethylene glycol monomethyl ether is 1: 1, contains one mole in one liter of electrolyte
(263g)Li[CF3SO2)2N]。
Embodiment eight: the lithium-sulfur cell preparation of carbon-coated nano boron lithium
Glucose (6g), urea (1g), lithium metaborate (3g) is taken to be added into 100mL deionized water, ultrasonic vibration mixing
30 minutes formation solution；Solidify 6 hours formation presomas after spray drying at 106 DEG C.Presoma is protected in nitrogen atmosphere
Under be warming up to 500 DEG C and be carbonized, after carbonization 2 hours, be heated to 1300 DEG C with the heating rate of 10 DEG C/min, constant temperature 2 hours,
It is cooled to room temperature and forms carbon-coated nano boron lithium composite material.
Take binder solution (1g) obtained in acetylene black, above-mentioned carbon-coated nano boron lithium (0.85g) and embodiment three, carbon
Nanometer boron lithium, acetylene black, Arabic gum nmp solution, in mass ratio 85: 10: 100 mixed grindings are coated, is applied after being modulated into paste
It is applied on copper film；In 100Kg cm after drying in the shade-2Pressure under compression moulding, obtain carbon-coated nano boron lithium cathode sheet.
Sulfur electrode obtained in embodiment six (taking diameter is the disk of 18mm) is placed in city and buys to resell button cell shell
(CR2025) in, sulfur electrode substrate aluminium film is contacted with by battery case；City dealer microporous polypropylene membrane (diameter 19mm) is set
On sulfur electrode；Above-mentioned cladding nanometer boron lithium cathode sheet (taking diameter is the disk of 18mm) is placed on diaphragm；It is straight on pad
After the foam nickel sheet that diameter is 18mm, thickness 1mm, voidage are 98%, electrolyte 0.2mL is added, it is close after encryption seal and battery cover
Envelope obtains the lithium-sulfur cell of cladding nanometer boron lithium.Electrolyte is with Li [CF3SO2)2N] (LiTFSI) be solute, dioxolanes
(C3H6O2) and ethylene glycol monomethyl ether (C4H10O2) mixture be solvent, the volume ratio of dioxolanes and ethylene glycol monomethyl ether is 1: 1,
Contain one mole of (263g) Li [CF in one liter of electrolyte3SO2)2N]。
The lithium-sulfur cell of carbon-coated nano boron lithium of the present invention and the multiplying power of tradition lithium-sulfur cell obtained in embodiment seven are put
Electric curve is as shown in Fig. 2, Fig. 3 is the comparison of its cycle life, charge-discharge magnification 1C, C=1675mAh/g.
From figure 2 it can be seen that either low range or high-multiplying power discharge, the lithium sulphur of carbon-coated nano boron lithium of the present invention
Battery all shows the discharge capacity than traditional lithium-sulfur cell, illustrates since carbon-coated nano boron lithium of the present invention is in charge and discharge process
In will form surface passivation layer unlike lithium piece and hinder the insertion and deintercalation process of lithium on cathode, thus show higher
Embedding and removing speed.Since carbon-coated nano boron lithium surface does not form passivation layer, active sulfur is not also just consumed, thus is shown
Cycle life more better than traditional lithium-sulfur cell, as shown in Figure 3.
The above enumerated are only specific embodiments of the present invention for finally, it should also be noted that.Obviously, the present invention is unlimited
In above embodiments, acceptable there are many deformations.Those skilled in the art can directly lead from present disclosure
Out or all deformations for associating, it is considered as protection scope of the present invention.
Claims (3)
1. the preparation method of the carbon-coated nano boron lithium composite material for lithium-sulfur cell cathode, which is characterized in that including following
Step:
(1) glucose, urea and lithium metaborate are added in deionized water, ultrasonic vibration mixes 30 minutes, makes lithium metaborate, urine
Element and glucose dissolution；After solution is spray-dried, solidify 6 hours formation presomas at 106 DEG C；
The mass ratio of glucose, urea and lithium metaborate is the corresponding 100 mL deionized waters of 6: 1: 1~3,1g urea；
(2) presoma is warming up to 500 DEG C under nitrogen atmosphere protection, after constant temperature is carbonized 2 hours, at 900~1300 DEG C
Heating 2~10 hours, obtains carbon-coated nano boron lithium composite material.
2. the method according to claim 1, wherein the heating rate in rate-determining steps (2) after carbonization is 10
℃/min。
3. it is negative that the carbon-coated nano boron lithium composite material prepared using claim 1 the method further prepares lithium battery
The method of pole piece, which comprises the following steps:
(1) in mass ratio 95: 5 N-Methyl pyrrolidone and gummi arabicum pulveratum are weighed；Gummi arabicum pulveratum is added in NMP, stirring
Under be heated to 90 DEG C；Continue stirring 2 hours, obtains the nmp solution of Arabic gum, be cooled to room temperature spare；
(2) in mass ratio 85: 10: 100 carbon-coated nano boron lithium composite material, acetylene black and Arabic gum nmp solution are weighed,
It is modulated into paste after mixed grinding, is coated on copper film；In 100 Kg/cm after drying in the shade2Pressure under compression moulding, obtain lithium electricity
Pond negative electrode tab.
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|---|---|---|---|---|
| US4162352A (en) * | 1976-09-24 | 1979-07-24 | The United States Of America As Represented By The Secretary Of The Navy | Battery with boron-lithium alloy anode |
| JPS62139267A (en) * | 1985-12-11 | 1987-06-22 | Matsushita Electric Ind Co Ltd | Thermal battery |
| CN1472831A (en) * | 2003-06-19 | 2004-02-04 | 上海交通大学 | Cathode carbon material of lithium ion battery and preparing method thereof |
| CN102851561A (en) * | 2011-06-27 | 2013-01-02 | 北京有色金属研究总院 | Lithium boron alloy production process, and device thereof |
| CN103236521A (en) * | 2013-04-17 | 2013-08-07 | 天津华夏泓源实业有限公司 | Nickel-cobalt-lithium manganese positive electrode material with boron-lithium composite oxide clad on surface, and preparation method thereof |
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| US7005214B2 (en) * | 2001-11-02 | 2006-02-28 | Wilson Greatbatch Technologies, Inc. | Noble metals coated on titanium current collectors for use in nonaqueous Li/CFx cells |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4162352A (en) * | 1976-09-24 | 1979-07-24 | The United States Of America As Represented By The Secretary Of The Navy | Battery with boron-lithium alloy anode |
| JPS62139267A (en) * | 1985-12-11 | 1987-06-22 | Matsushita Electric Ind Co Ltd | Thermal battery |
| CN1472831A (en) * | 2003-06-19 | 2004-02-04 | 上海交通大学 | Cathode carbon material of lithium ion battery and preparing method thereof |
| CN102851561A (en) * | 2011-06-27 | 2013-01-02 | 北京有色金属研究总院 | Lithium boron alloy production process, and device thereof |
| CN103236521A (en) * | 2013-04-17 | 2013-08-07 | 天津华夏泓源实业有限公司 | Nickel-cobalt-lithium manganese positive electrode material with boron-lithium composite oxide clad on surface, and preparation method thereof |
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