CN104078647B - A kind of lithium ion battery negative and preparation method thereof and lithium ion battery - Google Patents
A kind of lithium ion battery negative and preparation method thereof and lithium ion battery Download PDFInfo
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- CN104078647B CN104078647B CN201310101344.7A CN201310101344A CN104078647B CN 104078647 B CN104078647 B CN 104078647B CN 201310101344 A CN201310101344 A CN 201310101344A CN 104078647 B CN104078647 B CN 104078647B
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- lithium ion
- ion battery
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- negative electrode
- electrolyte
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 84
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 84
- 238000002360 preparation method Methods 0.000 title abstract description 14
- 239000003792 electrolyte Substances 0.000 claims abstract description 56
- 238000000576 coating method Methods 0.000 claims abstract description 51
- 239000011248 coating agent Substances 0.000 claims abstract description 49
- 239000007773 negative electrode material Substances 0.000 claims abstract description 44
- 239000007784 solid electrolyte Substances 0.000 claims abstract description 34
- 239000011230 binding agent Substances 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 17
- 239000000126 substance Substances 0.000 claims abstract description 4
- 239000000463 material Substances 0.000 claims description 20
- 239000002002 slurry Substances 0.000 claims description 20
- 239000002904 solvent Substances 0.000 claims description 17
- -1 polytetrafluoroethylene Polymers 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
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000004743 Polypropylene Substances 0.000 claims description 5
- 239000011883 electrode binding agent Substances 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
- 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
- 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 7
- 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
- 239000007767 bonding agent Substances 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
- 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
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 239000007774 positive electrode material Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 2
- 239000006255 coating slurry Substances 0.000 description 2
- 230000007423 decrease 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
- 239000007788 liquid Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 230000001105 regulatory effect 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
- 230000008901 benefit 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
- 230000005611 electricity Effects 0.000 description 1
- 239000011267 electrode slurry Substances 0.000 description 1
- 238000005516 engineering process Methods 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
- 239000002296 pyrolytic carbon Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 150000003376 silicon Chemical class 0.000 description 1
- 239000007787 solid Substances 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
Landscapes
- 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 kind of lithium ion battery negative, comprise collector, negative electrode material layer and electrolyte coating, and electrolyte coating is between negative electrode material layer and collector; This electrolyte coating is made up of Ca-Ti ore type solid electrolyte and binding agent, and the chemical formula of 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
wo3.Present invention also offers the preparation method of this lithium ion battery negative and adopt the lithium ion battery of this negative pole.The mistake adopting the lithium ion battery of negative pole provided by the invention can tolerate repeatedly puts circulation, 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, is easy to operation.
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, thus application is extensive.At present, the negative electrode of lithium ion battery generally adopts the active material layer of individual layer, is made into slurry, is then coated in copper foil current collector and forms negative electrode after being mixed with binding agent, solvent etc. by graphite isoreactivity material.By this negative electrode and positive electrode, barrier film etc. through to reel or lamination forms battery core, then battery core is placed in battery case through fluid injection, ageing, change into, namely obtain lithium ion battery after partial volume.
A kind of lithium rechargeable battery and negative pole thereof are disclosed in CN102332556A, by coating inorganic filler between negative current collector and negative electrode material layer in this battery, this inorganic filler coating is made up of inorganic filler and binding agent, it can increase the resistance of negative pole, the power of short dot can be reduced when short circuit, increase the fail safe in battery short circuit situation.Although this battery can increase the fail safe in battery short circuit situation, in use still there is battery and cross the hidden danger of putting in it.
Current lithium ion battery in use must add protection circuit plate, puts row protection into overcharging and crossing.But due to the reason such as long storage periods and self discharge, cell voltage happens occasionally lower than the situation of 2.50V, serve as when putting to 0V, battery can have been caused to occur the situations such as bulging, internal resistance increase, capacity attenuation, have a strong impact on the normal use of battery.Battery is full of electricity and occurred to put and continuous several times (namely cross and put circulation) again after crossing and putting, serious infringement is had to battery performance, particularly lithium ion battery is applied to the field that electric automobile etc. requires Long-Time Service under serial or parallel connection state, cross and put circulation and can cause battery capacity rapid decay, can internal short-circuit of battery be caused time serious, cause battery failure and safety problem.
Summary of the invention
The invention solves lithium ion battery of the prior art to there is the problem of putting and even cross and put circulation and cause battery failure or there is the technical problem of 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, 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.
Present invention also offers the preparation method of described lithium ion battery negative, comprise the following steps:
S10, be mixed with electrolyte slurry by after Ca-Ti ore type solid electrolyte and binding agent, solvent; Described electrolyte slurry is coated on negative pole currect collecting surface, after dry roll-in, obtains the collector that surface has electrolyte coating;
S20, cathode size corresponding for negative electrode material layer is coated on the surface that surface that step S10 obtains has the collector of electrolyte coating, after dry roll-in, obtains described lithium ion battery negative.
Finally, the invention provides a kind of lithium ion battery, the barrier film comprising positive pole, negative pole and be arranged 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 arranging the special electrolyte coating containing Ca-Ti ore type solid electrolyte of one deck between collector and negative electrode material layer, adopt described perovskite solid electrolyte electronic conductivity with change in voltage feature jumpy, the problem of the decomposition of SEI film and negative current collector oxidation dissolution is effectively avoided by reversible ohmic polarization and open circuit effect, make the mistake adopting the lithium ion battery of this negative pole can tolerate repeatedly put circulation, thus ensure useful life and the security performance of battery.Meanwhile, the preparation method of lithium ion battery negative provided by the invention, technique is simple, is easy to operation.
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 arranging the special electrolyte coating containing Ca-Ti ore type solid electrolyte of one deck between collector and negative electrode material layer, adopt described perovskite solid electrolyte electronic conductivity with change in voltage feature jumpy, the problem of the decomposition of SEI film and negative current collector oxidation dissolution is effectively avoided by reversible ohmic polarization and open circuit effect, make the mistake adopting the lithium ion battery of this negative pole can tolerate repeatedly put circulation, thus ensure 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 to put to negative pole during about 0.3V and is increased to about 3.4V to lithium current potential, SEI film starts to decompose, cross to put to negative pole during about 0.2V and about 3.5V is increased to lithium current potential, negative copper foil starts oxidation dissolution, and copper ion migration is to positive electrode surface and reduce precipitation.Copper Foil oxidation causes cathode impedance to increase, and SEI film is destroyed when causing again charging to be needed to regenerate new SEI film, and battery fluid decomposes generation gas in this process, causes battery bulging, consumes lithium ion simultaneously, cause capacity to decline.Overdischarge pressure is lower and cross that to put cycle-index more, and the Cu of precipitation is more, thickness and internal resistance increase more, 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 ionic vacancies and electron hole, therefore possesses higher ionic conductivity, can be used for solid lithium battery.But when such material contacts with lithium and is in electronegative potential, lithium ion can embed such material and cause electronic conductivity sharply to increase, and this material still can keep perovskite structure simultaneously; On the other hand, when this material is in high potential, lithium ion can reversible deviate from, recover the characteristic of its lower electronic conductivity.Current potential difference residing for material causes the electronic conductivity generation order of magnitude (10
4) change be the distinguishing feature of this kind of material.
And in the present invention, just based on above consideration, by arranging one deck electrolyte coating between negative current collector and negative electrode material layer, containing above-mentioned Ca-Ti ore type solid electrolyte in this electrolyte coating, its effect specifically comprises: (1) is when normal battery operation, negative pole current potential is lower, and Ca-Ti ore type solid electrolyte material, owing to having higher electronic conductivity, can ensure the electron transmission of negative electrode material layer and current collector layers.(2) and when battery cross put time, negative pole current potential raises, the electronic conductivity of Ca-Ti ore type solid electrolyte material can sharply decline, the electron transmission of negative electrode material layer and current collector layers is limited greatly, ohmic polarization effect greatly reduces the current density of negative electrode, negative electrode current potential is polarized rapidly to high potential, even can cause the internal break of battery, thus can effectively prevent from battery from crossing putting.(3) when battery again charges after crossing and putting, Ca-Ti ore type solid electrolyte is embedding lithium again, recovers the electronic conductivity that it is higher, ensures that battery normally works in normal voltage range.In sum, in whole process, electrolyte coating between collector and negative electrode material layer effectively serves " switch " effect, by ohmic polarization and the open circuit effect of Ca-Ti ore type solid electrolyte, effectively avoids 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 adopting the battery of this negative pole can tolerate continuous several times is made to put circulation.
In the present invention, the median particle diameter of described Ca-Ti ore type solid electrolyte is 0.01 ~ 10 μm, is preferably 0.05 ~ 5 μm.
In described electrolyte coating, the content of described binding agent, without the need to 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 adopted can adopt the binding agent identical with 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 μm, and the thickness of negative electrode material layer is 50 ~ 200 μm.Namely the thickness of 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 adopted is that various that those skilled in the art commonly use can the negative electrode active material of doff lithium, such as, 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 in non-graphitic carbon, graphite or the charcoal obtained by high-temperature oxydation by polyyne family macromolecule material or pyrolytic carbon, coke, organic polymer sinter, active carbon one or more.As the common practise of those skilled in the art, when negative electrode active material adopts silicon class material, also containing conductive agent in described negative electrode material layer, it act as conventionally known to one of skill in the art, repeats no more herein.
The various negative electrode binder that binding agent is known to the skilled person, such as polythiophene can be selected from, 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, with the weight of negative electrode active material for benchmark, the content of binding agent is 0.01-10wt%.
Present invention also offers the preparation method of described lithium ion battery negative, comprise the following steps:
S10, be mixed with electrolyte slurry by after Ca-Ti ore type solid electrolyte and binding agent, solvent; Described electrolyte slurry is coated on negative pole currect collecting surface, after dry roll-in, obtains the collector that surface has electrolyte coating;
S20, cathode size corresponding for negative electrode material layer is coated on the surface that surface that step S10 obtains has the collector of electrolyte coating, after dry roll-in, obtains described lithium ion battery negative.The preparation method of lithium ion battery negative provided by the invention, technique is simple, is easy to operation.
Particularly, according to method of the present invention, the first electrolyte slurry of preparation containing Ca-Ti ore type solid electrolyte, and coated negative pole currect collecting surface, electrolyte coating can be formed after dry roll-in, then prepare cathode size, and be applied and electrolyte coating surface, can negative electrode material layer be formed after dry roll-in, namely obtain lithium ion battery negative provided by the invention.Due in the present invention, each layer slurry, after applying respectively, all can carry out dry roll-in, still have obvious interface between each layer of the lithium ion battery negative therefore finally obtained.
Wherein, described electrolyte slurry is by obtaining after Ca-Ti ore type solid electrolyte and binding agent, solvent, and cathode size then passes through to obtain 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 various solvents that this area preparation electrode slurry is conventional, such as can be selected from 1-METHYLPYRROLIDONE (NMP), dimethyl sulfoxide (DMSO), DMF, water, ethanol, acetone one or more.Wherein, during preparation electrolyte slurry, relative to the Ca-Ti ore type solid electrolyte of 100 weight portions, the consumption of solvent is 50 ~ 300 weight portions.And when preparing cathode size, relative to the negative electrode active material of 100 weight portions, the consumption of solvent is then 30 ~ 200 weight portions.
In the present invention, the method for coating slurry (comprising electrolyte slurry, cathode size) can adopt various slurry painting methods conventional in prior art, such as, 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, coating slurry mode is slit film, specifically comprises method electrolyte slurry being coated on collection liquid surface and cathode size being coated on electrolyte coating surface and all adopts 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, such as, can adopt Copper Foil, but be not limited to this.
Finally, the invention provides a kind of lithium ion battery, the barrier film comprising positive pole, negative pole and be arranged 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 clearly understand, 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, be 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 μm, and negative active core-shell material is modified artificial graphite, and median particle diameter is 15 μm.
(1) take water as solvent, with CMC and SBR for 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 slit device for coating, coating machine scraper spacing is regulated to be 30 μm, this electrolyte slurry is intermittently coated on Copper Foil (Copper Foil size: width 160mm equably, thickness 16 μm) two sides on, dry at 120 DEG C, and in roll squeezer, compressing tablet process is carried out under 5MPa pressure, obtain surface and there is the copper foil current collector that thickness is the electrolyte coating of 1 μm.
(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 stir in de-airing mixer, form the cathode size of stable uniform.Coating machine scraper spacing is regulated to be 420 μm, this cathode size is intermittently coated on the two sides of the electrolyte coating on the copper foil current collector surface that step (1) obtains equably, 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 μm, and the thickness of negative electrode material layer is 120 μm.
(3) adopt cobalt acid lithium be positive electrode active materials, add binding agent, conductive agent and solvent respectively, through batching, coating, drying, roll-in, cut after make positive pole; The polypropylene diaphragm being 20 μm by negative pole J1 obtained to this positive pole, step (2) and thickness is wound into the battery core of rectangular lithium ion battery, and seal in the rectangular cell aluminum hull of this battery core loading 5mm × 34mm × 50mm, make 053450 type lithium ion battery, then through fluid injection, ageing, change into, namely 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), employing median particle diameter is the Li of 0.2 μm
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), employing median particle diameter is the Li of 0.5 μm
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), employing median particle diameter is the Li of 0.3 μm
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), employing median particle diameter is the Li of 0.5 μm
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), makes the thickness of electrolyte coating in the lithium ion battery negative J6 obtained be 400nm, and the thickness of negative electrode material layer is 150 μm.
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), makes the thickness of electrolyte coating in the lithium ion battery negative J7 obtained be 15 μm, and the thickness of negative electrode material layer is 50 μm.
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 stir in de-airing mixer, form the cathode size of stable uniform.Regulate coating machine scraper spacing to be 420 μm, be intermittently coated on the two sides of copper foil current collector equably by this slurry, then 120 DEG C of oven dry, through roll-in, film-making, obtain the negative pole DJ1 of this comparative example.
Adopt cobalt acid lithium be positive electrode active materials, add binding agent, conductive agent and solvent respectively, through batching, coating, drying, roll-in, cut after make positive pole respectively; The polypropylene diaphragm being 20 μm by positive pole, negative pole DJ1 and thickness is wound into the battery core of rectangular lithium ion battery, and seal in the rectangular cell aluminum hull of this battery core loading 5mm × 34mm × 50mm, make 053450 type lithium ion battery, then through fluid injection, ageing, change into, namely obtain after partial volume the full battery DA1 of this comparative example.
Comparative example 2
Method disclosed in CN102332556A embodiment 1 is adopted to prepare the negative pole DJ2 of the present embodiment.
Adopt cobalt acid lithium be positive electrode active materials, add binding agent, conductive agent and solvent respectively, through batching, coating, drying, roll-in, cut after make positive pole respectively; The polypropylene diaphragm being 20 μm by positive pole, negative pole DJ2 and thickness is wound into the battery core of rectangular lithium ion battery, and seal in the rectangular cell aluminum hull of this battery core loading 5mm × 34mm × 50mm, make 053450 type lithium ion battery, then through fluid injection, ageing, change into, namely obtain after partial volume the full battery DA2 of this comparative example.
Performance test
Crossing and put loop test: A1-A7 and DA1-DA2 battery is respectively got 20, holding up on day BS-9300 secondary cell device for detecting performance, under 25 ± 1 DEG C of conditions, battery being carried out 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 10min; With 1mA(0.001C) be discharged to 0V; Be 1 circulation.Repeat this step, circulating, record each circulation constant-current discharge to capacity during 3.0V from first time, this capacity is the recovery capacity of circulation last time, and the ratio of this capacity and first discharge capacity is capacity restoration rate.Often organize the mean value that data get 20 batteries.
Test result is as shown in table 1.
Table 1
As can be seen 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 repeatedly puts 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 done within the spirit and principles in the present invention, equivalent replacement and improvement etc., all should be included within 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 μm.
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 μm, and the thickness of negative electrode material layer is 50 ~ 200 μm.
5. the lithium ion battery negative according to claim 1 or 4, is characterized in that, described negative electrode material layer comprises negative electrode active material and binding agent; Wherein said negative electrode active material be selected from material with carbon element, ashbury metal, silicon alloy, silicon, tin, germanium one or more.
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, with the weight of negative electrode active material for benchmark, the content of binding agent is 0.01-10wt%.
8. prepare a method for lithium ion battery negative as claimed in claim 1, it is characterized in that, comprise the following steps:
S10, be mixed with electrolyte slurry by after Ca-Ti ore type solid electrolyte and binding agent, solvent; Described electrolyte slurry is coated on negative pole currect collecting surface, after dry roll-in, obtains the collector that surface has electrolyte coating;
S20, cathode size corresponding for negative electrode material layer is coated on the surface that surface that step S10 obtains has the collector of electrolyte coating, after dry roll-in, obtains described lithium ion battery negative.
9. the method preparing lithium ion battery negative according to claim 8, is characterized in that, containing negative electrode active material, binding agent and solvent in described cathode size; Solvent in cathode size and the solvent in electrolyte slurry be selected from 1-METHYLPYRROLIDONE, dimethyl sulfoxide (DMSO), DMF, water, ethanol, acetone independently of one another one or more.
10. the method preparing lithium ion battery negative 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, the barrier film comprising positive pole, negative pole and be arranged between positive pole, negative pole, is characterized in that, described negative pole is the lithium ion battery negative described in any one of claim 1-7.
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