CN104078647A - Lithium ion battery negative electrode, preparing method of lithium ion battery negative electrode and lithium ion battery - Google Patents
Lithium ion battery negative electrode, preparing method of lithium ion battery negative electrode and lithium ion battery Download PDFInfo
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- CN104078647A CN104078647A CN201310101344.7A CN201310101344A CN104078647A CN 104078647 A CN104078647 A CN 104078647A CN 201310101344 A CN201310101344 A CN 201310101344A CN 104078647 A CN104078647 A CN 104078647A
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- lithium ion
- ion battery
- negative electrode
- negative
- electrolyte
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 85
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 85
- 238000000034 method Methods 0.000 title claims abstract description 16
- 239000003792 electrolyte Substances 0.000 claims abstract description 55
- 238000000576 coating method Methods 0.000 claims abstract description 50
- 239000011248 coating agent Substances 0.000 claims abstract description 48
- 239000007773 negative electrode material Substances 0.000 claims abstract description 44
- 239000007784 solid electrolyte Substances 0.000 claims abstract description 34
- 239000000126 substance Substances 0.000 claims abstract description 4
- 239000011230 binding agent Substances 0.000 claims description 25
- 239000002002 slurry Substances 0.000 claims description 22
- 239000000463 material Substances 0.000 claims description 20
- 239000002904 solvent Substances 0.000 claims description 17
- -1 polytetrafluoroethylene Polymers 0.000 claims description 15
- 238000002360 preparation method Methods 0.000 claims description 15
- 229910052744 lithium Inorganic materials 0.000 claims description 13
- 239000002174 Styrene-butadiene Substances 0.000 claims description 10
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 10
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000004743 Polypropylene Substances 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 229920001155 polypropylene Polymers 0.000 claims description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 4
- 230000004888 barrier function Effects 0.000 claims description 4
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 claims description 4
- 239000011883 electrode binding agent Substances 0.000 claims description 4
- 239000011115 styrene butadiene Substances 0.000 claims description 4
- 229910052684 Cerium Inorganic materials 0.000 claims description 3
- 229910052693 Europium Inorganic materials 0.000 claims description 3
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 3
- 229910052779 Neodymium Inorganic materials 0.000 claims description 3
- 229910052772 Samarium Inorganic materials 0.000 claims description 3
- 229910052788 barium Inorganic materials 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 229910052741 iridium Inorganic materials 0.000 claims description 3
- 229910052746 lanthanum Inorganic materials 0.000 claims description 3
- 229910052758 niobium Inorganic materials 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 229910052706 scandium Inorganic materials 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 229910052712 strontium Inorganic materials 0.000 claims description 3
- 229910052715 tantalum Inorganic materials 0.000 claims description 3
- 229920000178 Acrylic resin Polymers 0.000 claims description 2
- 239000004925 Acrylic resin Substances 0.000 claims description 2
- 229920002799 BoPET Polymers 0.000 claims description 2
- 239000001856 Ethyl cellulose Substances 0.000 claims description 2
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 claims description 2
- 239000005041 Mylar™ Substances 0.000 claims description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 2
- 239000005062 Polybutadiene Substances 0.000 claims description 2
- 239000004698 Polyethylene Substances 0.000 claims description 2
- 239000004793 Polystyrene Substances 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- 229910000676 Si alloy Inorganic materials 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 2
- 229920002678 cellulose Polymers 0.000 claims description 2
- 239000001913 cellulose Substances 0.000 claims description 2
- 235000010980 cellulose Nutrition 0.000 claims description 2
- 229920006026 co-polymeric resin Polymers 0.000 claims description 2
- 239000003822 epoxy resin Substances 0.000 claims description 2
- 229920001249 ethyl cellulose Polymers 0.000 claims description 2
- 235000019325 ethyl cellulose Nutrition 0.000 claims description 2
- 229910052732 germanium Inorganic materials 0.000 claims description 2
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 2
- 239000004816 latex Substances 0.000 claims description 2
- 229920000126 latex Polymers 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 238000010422 painting Methods 0.000 claims description 2
- 229920001568 phenolic resin Polymers 0.000 claims description 2
- 239000005011 phenolic resin Substances 0.000 claims description 2
- 229920001992 poloxamer 407 Polymers 0.000 claims description 2
- 229920002401 polyacrylamide Polymers 0.000 claims description 2
- 229920002857 polybutadiene Polymers 0.000 claims description 2
- 229920000647 polyepoxide Polymers 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- 229920000128 polypyrrole Polymers 0.000 claims description 2
- 229920002223 polystyrene Polymers 0.000 claims description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 2
- 229920000123 polythiophene Polymers 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 2
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 2
- 238000005507 spraying Methods 0.000 claims description 2
- 239000011135 tin Substances 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- 239000007767 bonding agent Substances 0.000 abstract description 5
- 230000008569 process Effects 0.000 abstract description 3
- 230000008901 benefit Effects 0.000 abstract description 2
- 238000007599 discharging Methods 0.000 abstract 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 9
- 239000011889 copper foil Substances 0.000 description 9
- 230000008859 change Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 5
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 5
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000012530 fluid Substances 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 230000032683 aging Effects 0.000 description 4
- 239000006258 conductive agent Substances 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 4
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- 239000011256 inorganic filler Substances 0.000 description 4
- 229910003475 inorganic filler Inorganic materials 0.000 description 4
- 230000010287 polarization Effects 0.000 description 4
- 230000002441 reversible effect Effects 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 208000032953 Device battery issue Diseases 0.000 description 3
- 229910021102 Li0.5La0.5TiO3 Inorganic materials 0.000 description 3
- 239000002253 acid 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
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000007774 positive electrode material Substances 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000011267 electrode slurry Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002296 pyrolytic carbon Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 150000003376 silicon Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
Classifications
-
- 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
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
- H01M10/0562—Solid materials
-
- 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
-
- 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
-
- 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
-
- 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)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides a lithium ion battery negative electrode, which comprises a current collector, a negative electrode material layer and an electrolyte coating, wherein the electrolyte coating is positioned between the negative electrode material layer and the current collector and consists of perovskite type solid electrolytes and bonding agents, and the chemical formula of the perovskite type solid electrolytes is A<x>B<y>TiO<3>, A<x>B<y>Ta<2>O<6>, A<x>B<y>Nb<2>O<6> or A<h>M<k>D<n>Ti<w>O<3>. The invention also provides a preparing method of the lithium ion battery negative electrode and a lithium ion battery adopting the lithium ion battery negative electrode. The lithium ion battery adopting the lithium ion battery negative electrode provided by the invention can withstand multi-time over discharging cycles, and the service life and the safety performance of the battery are ensured. Meanwhile, the preparing method of the lithium ion battery negative electrode provided by the invention has the advantages that the process is simple, and the operation is easy.
Description
Technical field
The invention belongs to technical field of lithium ion, be specifically related to a kind of lithium ion battery negative and preparation method thereof and adopt the lithium ion battery of this lithium ion battery negative.
Background technology
Lithium ion battery because its specific capacity is high, operating voltage is high, operating temperature range is wide, self-discharge rate is low, have extended cycle life, the advantage such as pollution-free, lightweight, thereby application is extensive.At present, the negative electrode of lithium ion battery generally adopts the active material layer of individual layer, specifically after graphite isoreactivity material is mixed with binding agent, solvent etc., is made into slurry, is then coated on Copper Foil collector and forms negative electrode.By this negative electrode and positive electrode, barrier film etc. through reeling or lamination forms battery core, then battery core is placed in battery case through fluid injection, ageing, change into, obtain lithium ion battery after partial volume.
A kind of lithium rechargeable battery and negative pole thereof are disclosed in CN102332556A, in this battery, pass through coating inorganic filler between negative current collector and negative electrode material layer, this inorganic filler coating is made up of inorganic filler and binding agent, it can increase the resistance of negative pole, in short circuit, can reduce the power of short dot, increase the fail safe in battery short circuit situation.Although this battery can increase the fail safe in battery short circuit situation, it in use still exists battery to cross the hidden danger of putting.
Lithium ion battery in use must add protection circuit plate at present, protects overcharging and cross to put into go.But due to reasons such as long-term storage and self discharges, cell voltage happens occasionally lower than the situation of 2.50V, has served as while putting to 0 V, can cause battery to occur the situations such as bulging, internal resistance increase, capacity attenuation having a strong impact on the normal use of battery.Battery is full of electricity also continuous several times (cross and put circulation) occurred to put again after crossing and putting, battery performance is had to serious infringement, particularly lithium ion battery is applied to the long-term field using of the requirements such as electric automobile under serial or parallel connection state, cross and put circulation and can cause battery capacity to decay fast, when serious, internal short-circuit of battery be can cause, battery failure and safety problem caused.
Summary of the invention
The invention solves lithium ion battery of the prior art existed the problem of putting even excessively to put the technical problem that circulation causes battery failure or has potential safety hazard.
For the problems referred to above, the invention provides a kind of lithium ion battery negative, described lithium ion battery negative comprises collector, negative electrode material layer and electrolyte coating, described electrolyte coating is between negative electrode material layer and collector; Described electrolyte coating is made up of Ca-Ti ore type solid electrolyte and binding agent, and the chemical formula of described Ca-Ti ore type solid electrolyte is A
xb
ytiO
3, A
xb
yta
2o
6, A
xb
ynb
2o
6or A
hm
kd
nti
wo
3, wherein x+3y=2, h+2k+5n+4w=6,0 < x < 2,0 < y < 2/3, h, k, n, w are all greater than 0; A is at least one in Li, Na element, and B is at least one in La, Ce, Pr, Y, Sc, Nd, Sm, Eu, Gd element, and M is at least one in Sr, Ca, Ba, Ir, Pt element, and D is at least one in Nb, Ta element.
The present invention also provides the preparation method of described lithium ion battery negative, comprises the following steps:
S10, will after Ca-Ti ore type solid electrolyte and binding agent, solvent, be mixed with electrolyte slurry; Described electrolyte slurry is coated on to negative pole currect collecting surface, after dry roll-in, obtains surface and have the collector of electrolyte coating;
S20, cathode size corresponding negative electrode material layer is coated on to surface that step S10 obtains and has the surface of the collector of electrolyte coating, after dry roll-in, obtain described lithium ion battery negative.
Finally, the invention provides a kind of lithium ion battery, comprise positive pole, negative pole and be arranged at the barrier film between positive pole, negative pole, described negative pole is lithium ion battery negative provided by the invention.
Lithium ion battery negative provided by the invention, by the special electrolyte coating that contains Ca-Ti ore type solid electrolyte of one deck is set between collector and negative electrode material layer, adopt described perovskite solid electrolyte electronic conductivity with change in voltage feature jumpy, effectively avoided the problem of the decomposition of SEI film and negative current collector oxidation dissolution by reversible ohmic polarization and the effect of opening circuit, the mistake that the lithium ion battery that adopts this negative pole can be tolerated is repeatedly put circulation, thereby ensures useful life and the security performance of battery.Meanwhile, the preparation method of lithium ion battery negative provided by the invention, technique is simple, easy operating.
Embodiment
The invention provides a kind of lithium ion battery negative, described lithium ion battery negative comprises collector, negative electrode material layer and electrolyte coating, and described electrolyte coating is between negative electrode material layer and collector; Described electrolyte coating is made up of Ca-Ti ore type solid electrolyte and binding agent, and the chemical formula of described Ca-Ti ore type solid electrolyte is A
xb
ytiO
3, A
xb
yta
2o
6, A
xb
ynb
2o
6or A
hm
kd
nti
wo
3, wherein x+3y=2, h+2k+5n+4w=6,0 < x < 2,0 < y < 2/3, h, k, n, w are all greater than 0; A is at least one in Li, Na element, and B is at least one in La, Ce, Pr, Y, Sc, Nd, Sm, Eu, Gd element, and M is at least one in Sr, Ca, Ba, Ir, Pt element, and D is at least one in Nb, Ta element.
Lithium ion battery negative provided by the invention, by the special electrolyte coating that contains Ca-Ti ore type solid electrolyte of one deck is set between collector and negative electrode material layer, adopt described perovskite solid electrolyte electronic conductivity with change in voltage feature jumpy, effectively avoided the problem of the decomposition of SEI film and negative current collector oxidation dissolution by reversible ohmic polarization and the effect of opening circuit, the mistake that the lithium ion battery that adopts this negative pole can be tolerated is repeatedly put circulation, thereby ensures useful life and the security performance of battery.
Particularly, the present inventor finds, lithium ion battery of the prior art can not tolerate to be put circulation and causes the main cause of battery failure to be: lithium ion battery is crossed while putting to 0.3 V left and right negative pole to lithium potential rise to 3.4 V left and right, SEI film starts to decompose, cross while putting to 0.2V left and right negative pole to lithium potential rise to 3.5V left and right, negative copper foil starts oxidation dissolution, and copper ion migration is separated out to anodal surface reduction.Copper Foil oxidation causes that negative pole impedance increases, and SEI film is destroyed need to regenerate new SEI film while causing again charging, and in this process, battery fluid decomposes and produces gas, causes battery bulging, consumes lithium ion simultaneously, causes capacity loss.Overdischarge is pressed lower and is crossed that to put cycle-index more, and the Cu separating out is more, and thickness and internal resistance increase are more, and capacity restoration rate is lower.
Inventor finds, A
xb
ytiO
3, A
xb
yta
2o
6, A
xb
ynb
2o
6or A
hm
kd
nti
wo
3material has more ion room and electron hole, therefore possesses higher ionic conductivity, can be used for solid lithium battery.But such material contacts with lithium and in the time of electronegative potential, lithium ion can embed such material and cause that electronic conductivity sharply increases, this material still can keep perovskite structure simultaneously; On the other hand, when this material is during in high potential, lithium ion can be reversible be deviate from, and recovers the characteristic of its lower electronic conductivity.Material current potential difference of living in causes the electronic conductivity generation order of magnitude (10
4) variation be the distinguishing feature of this class material.
And in the present invention, just based on above consideration, by one deck electrolyte coating is set between negative current collector and negative electrode material layer, in this electrolyte coating, contain above-mentioned Ca-Ti ore type solid electrolyte, its effect specifically comprises: when normally work when battery (1), negative pole current potential is lower, and Ca-Ti ore type solid electrolyte material, owing to having higher electronic conductivity, can ensure the electronics transmission of negative electrode material layer and current collector layers.And cross while putting when battery (2), negative pole potential rise, the electronic conductivity of Ca-Ti ore type solid electrolyte material can sharply decline, the electronics transmission of negative electrode material layer and current collector layers is limited greatly, ohmic polarization effect has reduced the current density of negative electrode greatly, negative electrode current potential is polarized rapidly to high potential, even can cause the internal break of battery, thereby can effectively prevent that battery from crossing puts.(3) in the time that battery again charges after excessively putting, Ca-Ti ore type solid electrolyte is embedding lithium again, recovers its higher electronic conductivity, and guarantee battery is normally worked in normal voltage range.In sum, in whole process, electrolyte coating between collector and negative electrode material layer has effectively played " switch " effect, by the ohmic polarization of Ca-Ti ore type solid electrolyte and the effect of opening circuit, has effectively avoided the problem of the decomposition of SEI film and negative current collector oxidation dissolution; Simultaneously by the reversible action of Ca-Ti ore type solid electrolyte, the mistake that makes to adopt the battery of this negative pole can tolerate continuous several times is put circulation.
In the present invention, the median particle diameter of described Ca-Ti ore type solid electrolyte is 0.01 ~ 10 μ m, is preferably 0.05 ~ 5 μ m.
In described electrolyte coating, the content of described binding agent, without too much, only needs it Ca-Ti ore type solid electrolyte can be adhered to collection liquid surface and does not come off.Under preferable case, in described electrolyte coating, the content of Ca-Ti ore type solid electrolyte is 65 ~ 99.5wt%, and the content of binding agent is 0.5 ~ 35wt%.In electrolyte coating, the kind of the binding agent adopting can adopt and binding agent identical in negative electrode material layer, and the present invention is not particularly limited.
In the present invention, the thickness of described electrolyte coating is 5nm ~ 15 μ m, and the thickness of negative electrode material layer is 50 ~ 200 μ m.The thickness that is electrolyte coating can not be excessive, otherwise can reduce energy density and the high rate performance of battery.
The component of described negative electrode material layer is conventionally known to one of skill in the art, comprises negative electrode active material and binding agent.Wherein, the negative electrode active material adopting is the various negative electrode active materials that can doff lithium that those skilled in the art commonly use, for example, can be selected from one or more in material with carbon element, ashbury metal, silicon alloy, silicon, tin, germanium.Wherein said material with carbon element can adopt one or more in non-graphitic carbon, graphite or the charcoal being obtained by high-temperature oxydation by polyyne family macromolecule material or pyrolytic carbon, coke, organic polymer sinter, active carbon.As those skilled in the art's common practise, in the time that negative electrode active material adopts silicon class material, in described negative electrode material layer, also contain conductive agent, it act as conventionally known to one of skill in the art, repeats no more herein.
The various negative pole binding agents that binding agent is known to the skilled person, for example can be selected from polythiophene, polypyrrole, polytetrafluoroethylene, Kynoar, polyethylene, polypropylene, polystyrene, polyacrylamide, ethylene-propylene-diene copolymer resins, styrene butadiene ribber, polybutadiene, fluorubber, Pluronic F-127, polyvinylpyrrolidone, mylar, acrylic resin, phenolic resins, epoxy resin, polyvinyl alcohol, carboxy-propyl cellulose, ethyl cellulose, sodium carboxymethylcellulose (CMC), one or more in styrene-butadiene latex (SBR).As previously mentioned, the binding agent in electrolyte coating is also selected from aforementioned various binding agent.Under preferable case, in described negative electrode material layer, taking the weight of negative electrode active material as benchmark, the content of binding agent is 0.01-10wt%.
The present invention also provides the preparation method of described lithium ion battery negative, comprises the following steps:
S10, will after Ca-Ti ore type solid electrolyte and binding agent, solvent, be mixed with electrolyte slurry; Described electrolyte slurry is coated on to negative pole currect collecting surface, after dry roll-in, obtains surface and have the collector of electrolyte coating;
S20, cathode size corresponding negative electrode material layer is coated on to surface that step S10 obtains and has the surface of the collector of electrolyte coating, after dry roll-in, obtain described lithium ion battery negative.The preparation method of lithium ion battery negative provided by the invention, technique is simple, easy operating.
Particularly, the method according to this invention, the electrolyte slurry that first preparation contains Ca-Ti ore type solid electrolyte, and coated negative pole currect collecting surface, after dry roll-in, can form electrolyte coating, then prepare cathode size, and applied and electrolyte coating surface, after dry roll-in, can form negative electrode material layer, obtain lithium ion battery negative provided by the invention.In the present invention, each layer of slurry, after applying respectively, all can be dried roll-in, between each layer of the lithium ion battery negative that therefore finally obtains, still has obvious interface.
Wherein, described electrolyte slurry is by obtaining after Ca-Ti ore type solid electrolyte and binding agent, solvent, and cathode size is by obtaining after negative electrode active material and binding agent, solvent.In the present invention, solvent for preparation electrolyte slurry and cathode size is not particularly limited, adopt the conventional various solvents of this area preparation electrode slurry, for example can be selected from one or more in 1-METHYLPYRROLIDONE (NMP), dimethyl sulfoxide (DMSO), DMF, water, ethanol, acetone.Wherein, when preparation electrolyte slurry, with respect to the Ca-Ti ore type solid electrolyte of 100 weight portions, the consumption of solvent is 50 ~ 300 weight portions.And preparation is when cathode size, with respect to the negative electrode active material of 100 weight portions, the consumption of solvent is 30 ~ 200 weight portions.
In the present invention, the method that applies slurry (comprising electrolyte slurry, cathode size) can adopt various slurry painting methods conventional in prior art, for example, can be selected from any one in spraying, roller coat or slit coating method.As a kind of preferred implementation of the present invention, in the present invention, applying slurry mode is slit film, specifically comprises electrolyte slurry is coated on to collection liquid surface and the method that cathode size is coated on electrolyte coating surface is all adopted to slit film, but be not limited to this.The concrete operation step of slit film and process control condition are conventionally known to one of skill in the art, repeat no more herein.
In the present invention, the negative current collector that described collector is known to the skilled person, for example, can adopt Copper Foil, but be not limited to this.
Finally, the invention provides a kind of lithium ion battery, comprise positive pole, negative pole and be arranged at the barrier film between positive pole, negative pole, described negative pole is lithium ion battery negative provided by the invention.Lithium ion battery provided by the invention, has good resistance to mistake and puts cycle performance.
In order to make technical problem solved by the invention, technical scheme and beneficial effect clearer, below in conjunction with embodiment, the present invention is further elaborated.Should be appreciated that specific embodiment described herein, only in order to explain the present invention, is not intended to limit the present invention.
Embodiment 1
Ca-Ti ore type solid electrolyte material is Li
0.5la
0.5tiO
3, median particle diameter is 0.2 μ m, and negative active core-shell material is modified artificial graphite, and median particle diameter is 15 μ m.
(1) taking water as solvent, taking CMC and SBR as binding agent, by Li
0.5la
0.5tiO
3: the weight ratio preparation electrolyte slurry of CMC:SBR: water=100:5:5:200; This electrolyte slurry of 2L is placed in to slit device for coating, regulating coating machine scraper spacing is 30 μ m, this electrolyte slurry is intermittently coated on to Copper Foil (Copper Foil size: width 160mm equably, on thickness 16 μ two sides m), at 120 DEG C, dry, and under 5MPa pressure, in roll squeezer, carry out compressing tablet processing, obtain surface and there is the Copper Foil collector that thickness is the electrolyte coating of 1 μ m.
(2) by 940 grams of negative electrode active material Delaniums (94wt%), 30 grams of bonding agent CMC(3wt%) and 30 grams of bonding agent SBR(3wt%) join in 1200 grams of water, then in de-airing mixer, stir, form the cathode size of stable uniform.Regulating coating machine scraper spacing is 420 μ m, this cathode size is intermittently coated on equably on the two sides of electrolyte coating of the Copper Foil collection liquid surface that step (1) obtains, then 120 DEG C of oven dry, and through roll-in film-making, obtain the lithium ion battery negative J1 of the present embodiment, wherein the thickness of electrolyte coating is 1 μ m, and the thickness of negative electrode material layer is 120 μ m.
(3) adopting cobalt acid lithium is positive electrode active materials, adds respectively binding agent, conductive agent and solvent, makes positive pole through batching, coating, dry, roll-in, after cutting; The negative pole J1 that this positive pole, step (2) are made and thickness are the battery core that the polypropylene diaphragm of 20 μ m is wound into rectangular lithium ion battery, and this battery core is packed in the rectangular cell aluminum hull of 5mm × 34mm × 50mm and seal, make 053450 type lithium ion battery, then through fluid injection, ageing, change into, obtain after partial volume the lithium ion battery A1 of the present embodiment.
Embodiment 2
Adopt the step identical with embodiment 1 to prepare lithium ion battery negative J2 and the lithium ion battery A2 of the present embodiment, difference is:
In step (1), adopting median particle diameter is the Li of 0.2 μ m
0.32la
0.56nb
2o
6ca-Ti ore type solid electrolyte material as the present embodiment replaces the Li in embodiment 1
0.5la
0.5tiO
3.
Embodiment 3
Adopt the step identical with embodiment 1 to prepare lithium ion battery negative J3 and the lithium ion battery A3 of the present embodiment, difference is:
In step (1), adopting median particle diameter is the Li of 0.5 μ m
0.25na
0.1ce
0.55nb
2o
6ca-Ti ore type solid electrolyte material as the present embodiment replaces the Li in embodiment 1
0.5la
0.5tiO
3.
Embodiment 4
Adopt the step identical with embodiment 1 to prepare lithium ion battery negative J4 and the lithium ion battery A4 of the present embodiment, difference is:
In step (1), adopting median particle diameter is the Li of 0.3 μ m
0.2pr
0.5y
0.1tiO
3ca-Ti ore type solid electrolyte material as the present embodiment replaces the Li in embodiment 1
0.5la
0.5tiO
3.
Embodiment 5
Adopt the step identical with embodiment 1 to prepare lithium ion battery negative J5 and the lithium ion battery A5 of the present embodiment, difference is:
In step (1), adopting median particle diameter is the Li of 0.5 μ m
0.3sr
0.6nb
0.5ti
0.5o
3ca-Ti ore type solid electrolyte material as the present embodiment replaces the Li in embodiment 1
0.5la
0.5tiO
3.
Embodiment 6
Adopt the step identical with embodiment 1 to prepare lithium ion battery negative J5 and the lithium ion battery A5 of the present embodiment, difference is:
In step (1), weight ratio Li
0.5la
0.5tiO
3: SBR=100:50.
Embodiment 7
Adopt the step identical with embodiment 1 to prepare lithium ion battery negative J6 and the lithium ion battery A6 of the present embodiment, difference is:
Scraper spacing in set-up procedure (1), (2), in the lithium ion battery negative J6 that makes to obtain, the thickness of electrolyte coating is 400nm, the thickness of negative electrode material layer is 150 μ m.
Embodiment 8
Adopt the step identical with embodiment 1 to prepare lithium ion battery negative J7 and the lithium ion battery A7 of the present embodiment, difference is:
Scraper spacing in set-up procedure (1), (2), in the lithium ion battery negative J7 that makes to obtain, the thickness of electrolyte coating is 15 μ m, the thickness of negative electrode material layer is 50 μ m.
Comparative example 1
By 940 grams of negative electrode active material Delaniums (94wt%), 30 grams of bonding agent CMC(3wt%) and 30 grams of bonding agent SBR(3wt%) join in 1200 grams of water, then in de-airing mixer, stir, form the cathode size of stable uniform.Regulating coating machine scraper spacing is 420 μ m, and this slurry is intermittently coated on the two sides of Copper Foil collector equably, and then 120 DEG C of oven dry, through roll-in, film-making, obtain the negative pole DJ1 of this comparative example.
Adopting cobalt acid lithium is positive electrode active materials, adds respectively binding agent, conductive agent and solvent, makes respectively positive pole through batching, coating, dry, roll-in, after cutting; The polypropylene diaphragm that is 20 μ m by positive pole, negative pole DJ1 and thickness is wound into the battery core of rectangular lithium ion battery, and this battery core is packed in the rectangular cell aluminum hull of 5mm × 34mm × 50mm and seal, make 053450 type lithium ion battery, then through fluid injection, ageing, change into, obtain after partial volume the full battery DA1 of this comparative example.
Comparative example 2
Adopt CN102332556A embodiment 1 disclosed method to prepare the negative pole DJ2 of the present embodiment.
Adopting cobalt acid lithium is positive electrode active materials, adds respectively binding agent, conductive agent and solvent, makes respectively positive pole through batching, coating, dry, roll-in, after cutting; The polypropylene diaphragm that is 20 μ m by positive pole, negative pole DJ2 and thickness is wound into the battery core of rectangular lithium ion battery, and this battery core is packed in the rectangular cell aluminum hull of 5mm × 34mm × 50mm and seal, make 053450 type lithium ion battery, then through fluid injection, ageing, change into, obtain after partial volume the full battery DA2 of this comparative example.
Performance test
Cross and put loop test: A1-A7 and DA1-DA2 battery are respectively got to 20, holding up on day BS-9300 secondary cell device for detecting performance, under 25 ± 1 DEG C of conditions, battery is carried out to charge and discharge cycles test with 0.2C.Step is as follows: shelve 10min; Constant voltage charge ends to 4.2V/0.05C; Shelve 10min; Constant-current discharge is to 3.0V; Shelve 10 min; With 1mA(0.001C) be discharged to 0V; Be 1 circulation.Repeat this step, from circulating for the first time, the capacity while recording each circulation constant-current discharge to 3.0V, this capacity is the recovery capacity of circulation last time, and this capacity and the first ratio of discharge capacity are capacity restoration rate.Every group of data are got the mean value of 20 batteries.
Test result is as shown in table 1.
Table 1
。
Can find out from the test result of upper table 1, adopt the lithium ion battery of negative pole provided by the invention, the mistake that can tolerate is repeatedly put circulation.Although add inorganic filler layer in DA2 in negative pole, it only can increase negative pole resistance, improves the fail safe in battery short circuit situation, crosses the problem of putting without any improvement for battery.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any amendments of doing within the spirit and principles in the present invention, be equal to and replace and improvement etc., within all should being included in protection scope of the present invention.
Claims (11)
1. a lithium ion battery negative, is characterized in that, described lithium ion battery negative comprises collector, negative electrode material layer and electrolyte coating, and described electrolyte coating is between negative electrode material layer and collector; Described electrolyte coating is made up of Ca-Ti ore type solid electrolyte and binding agent, and the chemical formula of described Ca-Ti ore type solid electrolyte is A
xb
ytiO
3, A
xb
yta
2o
6, A
xb
ynb
2o
6or A
hm
kd
nti
wo
3, wherein x+3y=2, h+2k+5n+4w=6,0 < x < 2,0 < y < 2/3, h, k, n, w are all greater than 0; A is at least one in Li, Na element, and B is at least one in La, Ce, Pr, Y, Sc, Nd, Sm, Eu, Gd element, and M is at least one in Sr, Ca, Ba, Ir, Pt element, and D is at least one in Nb, Ta element.
2. lithium ion battery negative according to claim 1, is characterized in that, the median particle diameter of described Ca-Ti ore type solid electrolyte is 0.01 ~ 10 μ m.
3. lithium ion battery negative according to claim 1, is characterized in that, in described electrolyte coating, the content of Ca-Ti ore type solid electrolyte is 65 ~ 99.5wt%, and the content of binding agent is 0.5 ~ 35wt%.
4. lithium ion battery negative according to claim 1, is characterized in that, the thickness of described electrolyte coating is 5nm ~ 15 μ m, and the thickness of negative electrode material layer is 50 ~ 200 μ m.
5. according to the lithium ion battery negative described in claim 1 or 4, it is characterized in that, described negative electrode material layer comprises negative electrode active material and binding agent; Wherein said negative electrode active material is selected from one or more in material with carbon element, ashbury metal, silicon alloy, silicon, tin, germanium.
6. lithium ion battery negative according to claim 5, it is characterized in that, binding agent in described electrolyte coating and negative electrode material layer is selected from polythiophene independently of one another, polypyrrole, polytetrafluoroethylene, Kynoar, polyethylene, polypropylene, polystyrene, polyacrylamide, ethylene-propylene-diene copolymer resins, styrene butadiene ribber, polybutadiene, fluorubber, Pluronic F-127, polyvinylpyrrolidone, mylar, acrylic resin, phenolic resins, epoxy resin, polyvinyl alcohol, carboxy-propyl cellulose, ethyl cellulose, sodium carboxymethylcellulose, one or more in styrene-butadiene latex.
7. lithium ion battery negative according to claim 5, is characterized in that, in described negative electrode material layer, taking the weight of negative electrode active material as benchmark, the content of binding agent is 0.01-10wt%.
8. the preparation method of lithium ion battery negative claimed in claim 1, is characterized in that, comprises the following steps:
S10, will after Ca-Ti ore type solid electrolyte and binding agent, solvent, be mixed with electrolyte slurry; Described electrolyte slurry is coated on to negative pole currect collecting surface, after dry roll-in, obtains surface and have the collector of electrolyte coating;
S20, cathode size corresponding negative electrode material layer is coated on to surface that step S10 obtains and has the surface of the collector of electrolyte coating, after dry roll-in, obtain described lithium ion battery negative.
9. preparation method according to claim 8, is characterized in that, contains negative electrode active material, binding agent and solvent in described cathode size; Solvent in solvent and electrolyte slurry in cathode size is selected from one or more in 1-METHYLPYRROLIDONE, dimethyl sulfoxide (DMSO), DMF, water, ethanol, acetone independently of one another.
10. preparation method according to claim 8, is characterized in that, the painting method in step S10 and S20 is selected from spraying, roller coat or slit coating method independently of one another.
11. 1 kinds of lithium ion batteries, comprise positive pole, negative pole and are arranged at the barrier film between positive pole, negative pole, it is characterized in that, described negative pole is the lithium ion battery negative described in claim 1-7 any one.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102760860A (en) * | 2011-04-29 | 2012-10-31 | 三星电子株式会社 | Negative electrode for lithium secondary battery, method of manufacturing the same, and lithium secondary battery employing the same |
| CN103348525A (en) * | 2011-02-15 | 2013-10-09 | 索尼公司 | Solid electrolyte battery |
-
2013
- 2013-03-27 CN CN201310101344.7A patent/CN104078647B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103348525A (en) * | 2011-02-15 | 2013-10-09 | 索尼公司 | Solid electrolyte battery |
| CN102760860A (en) * | 2011-04-29 | 2012-10-31 | 三星电子株式会社 | Negative electrode for lithium secondary battery, method of manufacturing the same, and lithium secondary battery employing the same |
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