CN100452491C - Granular electrode composite material with positive temp coefficient and preparing process thereof - Google Patents
Granular electrode composite material with positive temp coefficient and preparing process thereof Download PDFInfo
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- CN100452491C CN100452491C CNB2006100199608A CN200610019960A CN100452491C CN 100452491 C CN100452491 C CN 100452491C CN B2006100199608 A CNB2006100199608 A CN B2006100199608A CN 200610019960 A CN200610019960 A CN 200610019960A CN 100452491 C CN100452491 C CN 100452491C
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- composite material
- electrode composite
- temperature coefficient
- polymer
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The invention discloses a grained electrode composite with positive temperature coefficient and the preparing method thereof. And the composite comprises kernel of active material and PTC shell, where the kernel mainly makes electrochemical reaction and provides battery capacity and the PTC mainly plays the role in safety protection of positive temperature coefficient. And the electrode made by the composite can sense temperature variation caused by overcurrent and short circuit in battery and in time increase impedance and reduce current to make the battery be in a safe state, preventing battery exploding or burning. When the battery temperature returns to normal, the resistance of the composite returns to lower value, assuring normal battery charge and discharge; and the composite has higher sensitivity and lower resistance value.
Description
Technical field
The present invention relates to a kind of electrode composite material and preparation method thereof, be applicable to various field of chemical power source with positive temperature coefficient, for power supply under overcurrent, excess temperature or internal circuit status, the safeguard protection effect is provided.Be particularly useful for existing the lithium secondary battery of potential safety hazard.
Background technology
Along with the development of society, mobile electronic product and electric tool engender, and provide the chemical power source of power to enjoy people's attention with it.Recent two decades, the development of chemical power source is very fast, and the specific energy and the specific power of battery improve constantly.Yet when pursuing battery performance, people more and more pay attention to the security performance of battery, as overcharge, under excess temperature or the over-current state, battery does not burn or explodes.
At the potential safety hazard of battery, many safety measures have been taked, as safety anti-explosive valve, overcharge protection circuit, outside PTC resistance, the inner chemical cycle of battery system etc.Yet these safety measures are general asynchronous with inside battery physicochemical change (as temperature, chemical substance burning etc.), and cause safeguard protection malfunctioning.And these potential safety hazards lithium secondary battery inflammable for adopting, explosive organic electrolyte is especially outstanding.At the particularity of lithium secondary battery safety, many guard methods have been proposed at present.As the charging controller of loaded ribbon protective circuit, the barrier film that safety valve, outside PTC resistance, inner employing heat-seal are set, electrolyte protection additive etc.But their exist the protection irreversibility or the timely shortcoming of reaction cell interior change, therefore, need seek a kind of measure to inside battery sensitiveness and reversible protectiveness.
PTC resistance is a kind of thermally sensitive reversible protective device.At United States Patent (USP) the 4th, 255, the external protector that adopts PTC resistance is disclosed in 98 and 5,592,068, produce battery to prevent battery overcurrent or excess temperature and damage or insecurity.Yet this device can not be made responsive judgement to the inside battery environment, and PTC resistance is when perceiving variation usually, and battery has been in the high-risk state.For reaching the internal temperature of battery sensitivity, inner PTC assembly principle has been proposed at present.A kind of secondary cell multi-layer electrode plate is disclosed in Chinese patent the 01219233.3rd, the material that wherein has positive temperature coefficient (PTC) character is between conduction collector plate and the electrode active material layers,, reduce or electric current that blocking-up is passed through owing to the variations in temperature that overcurrent or short circuit produce with perception inside battery at any time.And a kind of lithium secondary battery that contains ptc powder is also disclosed in Chinese patent the 200410080958.2nd, wherein will have ptc powder mixes with electrode activity powder, conductive agent, binding agent, make electrode jointly, to obtain thermally sensitive effect.Though these two kinds of methods can play the effect of internal temperature of battery sensitivity, the former PTC is a stratiform, and invisible having increased contacts with the conduction of matrix and the complexity of manufacturing process, and be bigger to the high rate performance influence of battery; The latter then PTC powder partly is dispersed in the electrode, and temperature sensitivity is reduced greatly.
Summary of the invention
At the problem that above method ran into, therefore the objective of the invention is to propose a kind of granular electrode composite material and preparation method thereof with positive temperature coefficient property.It can play the effect of electrode active material under normal charge status, play PTC effect in the time of causing temperature control at overcurrent or internal circuit again, and the partition electric current makes battery be returned to safe condition; Have higher responsive ability and lower resistance value.
Technical scheme
A kind of granular electrode composite material proposed by the invention with positive temperature coefficient, it is characterized in that: comprise one and can carry out electrochemical reaction and possess the kernel of the active material of charge-discharge performance, and one has the polymer composition that contains conductive particle of positive temperature coefficient (PTC) or the shell of inorganic composite oxide ptc material.
Above-mentioned granular electrode composite material with positive temperature coefficient is characterized in that: the shell of described ptc material accounts for 0.1～40% of electrode composite material quality.
Above-mentioned granular electrode composite material with positive temperature coefficient is characterized in that: the shell of described ptc material accounts for 5～10% of electrode composite material quality.Normal temperature this moment resistance down is less, and the PTC effect of while during high temperature is higher.
Above-mentioned granular electrode composite material with positive temperature coefficient is characterized in that: the active material core of described electrode composite material is can provide electrochemical reaction and the material that possesses charge-discharge performance, and this material is cobalt acid lithium LiCoO
2, LiMn2O4 LiMn
2O
4, trielement composite material LiCo
xNi
yMn
zO
2, LiFePO4 LiFePO
4, graphite, MCMB, tinbase composite material, hydroxide nickel (OH)
2, hydrogen bearing alloy, brown lead oxide or other can be used for one of electrode active material of chemical power source.
Above-mentioned granular electrode composite material with positive temperature coefficient is characterized in that: the ptc material shell of described electrode composite material is polymer composition or the inorganic composite oxide ptc material that contains conductive particle, as BaTiO
3, or the BaTiO that mixes
3Material; The composition that wherein contains the polymer composition of conductive particle comprises: (A) a kind of fusing point is at 80～180 ℃ polymer, and this polymer can be for the homopolymers or the copolymer of alkene and derivative thereof, as polyethylene, polyethylene/vinyl acetate etc., or epoxy resin; (B) a kind of conductive particle is as graphite, carbon black, other material with carbon element, metal powder.
Above-mentioned granular electrode composite material with positive temperature coefficient is characterized in that: described conductive particle accounts for 10～80% of composition quality.
Above-mentioned granular electrode composite material with positive temperature coefficient is characterized in that: described conductive particle accounts for 20～40% of composition quality.Normal temperature this moment resistance down is less, and the PTC effect of while during high temperature is higher.
In another aspect of this invention, the preparation method of this granular electrode composite material also is provided, the homopolymers or the copolymer of alkene and derivative thereof are dissolved in its good solvent, add conductive particle again, or directly existing polymer composition or the inorganic composite oxide ptc material that contains conductive particle is dissolved in its good solvent, after stirring, add granular active material, then solvent is removed, polymer is together with the surface of conductive particle attached to active material particle like this, form the shell of electrode material granules, and the active material particle that is wrapped up forms kernel.
The invention has the advantages that the material that will have positive temperature coefficient directly is coated on surface of active material, form granular combination electrode material with PTC performance.When constituting the pole plate of electrode with this granular combination electrode material, the PTC shell can directly be responded to active material and the variations in temperature of electrode under unconventional state, and responsive ability is better than additive method.Simultaneously, little to the conductivity influence of electrode material at normal temperatures because the ptc layer that coats is thinner, avoided additive method to adopt the considerable influence that electrode resistance is produced behind the ptc material.The granular combination electrode material that employing has the PTC performance manufactures electrode, can reflect the variations in temperature that inside battery causes owing to overcurrent, short circuit, in time increases impedance, reduces electric current, and battery is in a safe condition.When battery temperature is returned to just often, the resistance of combination electrode material also returns to than low value, guarantees normal battery charge and discharge.Therefore, this can be sensitive the perception internal temperature of battery electrode material that changes and have reversible protective value, protect for the excess temperature fail safe of battery provides to try hard to keep.
Description of drawings
Fig. 1 is the combination electrode material schematic diagram of drawing according to inventive concept with positive temperature coefficient.Wherein, combination electrode material 1, active material core 2, ptc material shell 3, conductive particle 4, polymer 5.
Fig. 2 is to have the resistance of combination electrode material of temperature coefficient and the graph of a relation of temperature in according to an embodiment of the present invention.
Concrete execution mode
At above accompanying drawing, by the description to execution mode, purpose of the present invention and intention can comparatively clearly show.
Fig. 1 shows the combination electrode material schematic diagram of drawing according to inventive concept with positive temperature coefficient.As shown in Figure 1, the granular combination electrode material 1 with positive temperature coefficient comprises active material core 2 and ptc material shell 3.Active material 2 mainly carries out electrochemical reaction, and the capacity of battery is provided.And ptc material 3 mainly is when internal temperature of battery increases, and it is big that resistance becomes, and reduces electric current, plays reversible safeguard protection effect.Ptc material shell 3 described in Fig. 1 mainly comprises conductive particle 4 and polymer 5.Conductive particle 4 can be graphite, carbon black, other material with carbon element, metal powder.And polymer 5 can be the homopolymers or the copolymer of alkene and derivative thereof, as polyethylene, polyethylene/vinyl acetate etc., or epoxy resin.
Above-mentioned granular electrode composite material with positive temperature coefficient, described kernel granularity be generally at the 1-20 micron, but also may diminish to tens nanometers, at this moment can be that a particle is nuclear, also may be that several particles are nuclear.
On making, process can be described as polymer 5 is dissolved in its good solvent usually, mixes the back and adds conductive particle 4, adds active material 2 then, remove good solvent after, the combination electrode material that promptly obtains having positive temperature coefficient.
In order to verify that the present invention has the PTC effect of the combination electrode material of positive temperature coefficient, embodiments of the invention are as follows:
Embodiment 1
In its good solvent kerosene, mix the back and add conductive particle 4: acetylene black adds active material 2:LiCoO then with polymer 5 polyethylene (PE) heat of solution
2The granularity of active material 2 is 6～15 microns, and shell 3 accounts for 5% of electrode composite material quality; After removing good solvent, promptly obtain having the granular combination electrode material of positive temperature coefficient.
Embodiment 2
Polymer 5: polyethylene (PE)
Good solvent: toluene
Conductive particle 4: acetylene black
Active material 2:LiFePO
4
The granularity of active material 2 is: 100～500 nanometers
What shell 3 accounted for the electrode composite material quality is: 8%.
Embodiment 3
Polymer 5: epoxy resin and curing agent
Good solvent: ethanol
Conductive particle 4: acetylene black
Active material 2:LiMn
2O
4
The granularity of active material is: 2～10 microns
What shell accounted for the electrode composite material quality is: 5%.
Fig. 2 demonstrates according to the resistance of the made electrode of granular combination electrode material that has temperature coefficient in the embodiments of the invention 1 and the graph of a relation of temperature.As shown in Figure 2, when temperature is low (room temperature～80 ℃), the resistance of combination electrode material lower (3 ohm), and when temperature continues to raise again, resistance also increases thereupon, when temperature reached 145 ℃, resistance (40 ohm) increased tens times than resistance under the normal temperature (3 ohm), shows good PTC performance.
More than part embodiment of the present invention is illustrated; but should be appreciated that these are described and execution mode only is for clearer the intent of the present invention and the thought of providing; understand technical scheme of the present invention; for those skilled in the art; can spirit do various changes and improvement according to the present invention, all should belong in the protection range of claim of the present invention.
Claims (6)
1, the granular electrode composite material that has positive temperature coefficient, it is characterized in that: comprise one and can carry out electrochemical reaction and possess the kernel of the active material of charge-discharge performance and conductive particle and the composition of polymer or the shell of inorganic composite oxide ptc material with positive temperature coefficient;
Described polymer is a fusing point at 80～180 ℃ polymer, and this polymer is the homopolymers or the copolymer of alkene and derivative thereof;
The shell of described ptc material accounts for 0.1～40% of electrode composite material quality.
2, have the granular electrode composite material of positive temperature coefficient according to claim 1, it is characterized in that: the shell of described ptc material accounts for 5～10% of electrode composite material quality.
3, have the granular electrode composite material of positive temperature coefficient according to claim 1, it is characterized in that: the active material core of described electrode composite material is can provide electrochemical reaction and the material that possesses charge-discharge performance, and this material is cobalt acid lithium LiCoO
2, LiMn2O4 LiMn
2O
4, trielement composite material LiCo
xNi
yMn
zO
2, LiFePO4 LiFePO
4, graphite, MCMB, tinbase composite material, hydroxide nickel (OH)
2, hydrogen bearing alloy, brown lead oxide or other can be used for one of electrode active material of chemical power source.
4, have the granular electrode composite material of positive temperature coefficient according to claim 1, it is characterized in that: described conductive particle accounts for 10～80% of composition quality.
5, the granular electrode composite material as having positive temperature coefficient as described in the claim 4, it is characterized in that: described conductive particle accounts for 20～40% of composition quality.
6, preparation method with granular electrode composite material of positive temperature coefficient as claimed in claim 1, it is characterized in that: with polymer dissolution in its good solvent, 10～80% the conductive particle that adds the composition quality of conductive particle and polymer again, or directly the composition of existing conductive particle and polymer is dissolved in the polymer good solvent, after stirring, the granular active material that adds electrode composite material quality 60～99.9%, then solvent is removed, polymer is together with the surface of conductive particle attached to active material particle like this, form the shell of electrode material granules, and the active material particle that is wrapped up forms kernel.
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| CN100452491C true CN100452491C (en) | 2009-01-14 |
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Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101136471B (en) * | 2006-08-30 | 2010-06-16 | 比亚迪股份有限公司 | Electrode active material and method for making same and lithium ion secondary battery electrode |
| CN102272987A (en) * | 2009-01-06 | 2011-12-07 | 株式会社Lg化学 | Positive electrode active material for lithium secondary battery |
| CN102265434B (en) * | 2009-01-06 | 2015-04-01 | 株式会社Lg化学 | Positive electrode active material for lithium secondary battery |
| CN101630729B (en) * | 2009-04-16 | 2011-03-30 | 华中科技大学 | Composite electrode materials for high power lithium secondary battery and preparation method thereof |
| CN101887960B (en) | 2010-07-13 | 2015-07-29 | 清华大学 | Lithium ion cell polar ear and there is the lithium ion battery of this lug |
| TWI418080B (en) * | 2010-07-16 | 2013-12-01 | Hon Hai Prec Ind Co Ltd | Lug of lithium ion battery and lithium ion battery using the same |
| CN105845968A (en) * | 2016-04-15 | 2016-08-10 | 惠州市聚鼎电子有限公司 | Safe battery and manufacturing method thereof |
| CN107706376A (en) * | 2017-09-25 | 2018-02-16 | 中国科学院过程工程研究所 | Coat hud typed composite positive pole, its preparation method and the purposes in lithium ion battery of thermistor material |
| CN112467071B (en) * | 2019-09-06 | 2022-11-04 | 青岛九环新越新能源科技股份有限公司 | Electrode material based on thermosensitive material and preparation method thereof |
| CN112054200A (en) * | 2020-09-08 | 2020-12-08 | 昆山宝创新能源科技有限公司 | Pyroelectric composite anode material and preparation method and application thereof |
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