CN101872878A - Method for enhancing floating resistance of lithium manganate lithium ion battery system - Google Patents
Method for enhancing floating resistance of lithium manganate lithium ion battery system Download PDFInfo
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- CN101872878A CN101872878A CN201010168630A CN201010168630A CN101872878A CN 101872878 A CN101872878 A CN 101872878A CN 201010168630 A CN201010168630 A CN 201010168630A CN 201010168630 A CN201010168630 A CN 201010168630A CN 101872878 A CN101872878 A CN 101872878A
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Abstract
The invention discloses a method for enhancing the floating resistance of a lithium manganate lithium ion battery system, which comprises the following steps: preparing a lithium manganate lithium ion battery and controlling an external protection circuit of the battery, wherein in the preparation process of the lithium manganate lithium ion battery, gas-phase silicon oxide or aluminum oxide of which the mass content is 0.5-15% is added to anode materials; and after a lithium manganate lithium ion battery pack is prepared, a lithium battery pack management system is arranged outside the battery pack to carry out an intermittent floating management on the battery. By synergistic effects generated by the method combining the internal structural change with the external circuit control, the invention enables the internal structure of the battery to be more stable, simultaneously reduces the possibility of electrolyte decomposition, gas generation and other defects which may occur in the battery, enhances the floating resistance of the lithium manganate lithium ion battery system, and greatly prolongs the cycle life of the battery.
Description
Technical field
The invention belongs to the lithium ion battery field, be specifically related to the method that a kind of manganate lithium ion battery system improves anti-floating charge ability.
Background technology
The general method of lead-acid battery that uses in the base station and lithium battery employing is at present, simply connecting between the battery, there is not external batteries management system BMS (Bttery ManagementSystern) that the voltage of each battery is managed, just by the power supply unit output voltage, stagnation pressure to battery system is controlled, so just cause each battery all to be under the full power state for a long time, under this state, not only damage the useful life of battery, cause a large amount of power wastages, and have certain potential safety hazard.
The reduction of battery cycle life mainly is because under fully charged state, both positive and negative polarity and electrolyte component in the system play pendulum, and both positive and negative polarity raw material and electrolyte itself is synthetic by redox reaction, the side reaction that the highly charged attitude of battery has increased side reaction generation on these inside battery electrodes and electrolyte inside takes place, the result causes subsiding of inside battery both positive and negative polarity raw material structure easily, with the decomposition of electrolyte, cause the inside aerogenesis of battery and the cycle life of battery to reduce.
Summary of the invention
The objective of the invention is to strengthen the method that the anode electrode material structure is stable and the external cell protection circuit is set by inside, the combination of inner and outside make lithium battery particularly lithium manganate battery have higher anti-floating charge ability, and improved battery and recycled the life-span 25%～35%.
Purpose of the present invention can reach by following measure:
A kind of method that improves floating resistance of lithium manganate lithium ion battery system, comprise the preparation of manganate lithium ion battery and the control of outside batteries protective circuit, when manganate lithium ion battery prepared, the adding mass content was 0.5～15% aerosil or alundum (Al in anodal material; After the preparation of manganate lithium ion battery group is finished,, battery is carried out the batch (-type) float management at battery pack outer setting lithium battery group management system.
The mass content of wherein anodal each component of material is a positive active material LiMn2O4 75%～96%, conductive agent 0.5～15%, and structural stabilizing agent 0.5～15%, bonding agent 2.5%～15%, each component sum is 100%; Wherein said structural stabilizing agent is aerosil or alundum (Al, and preferred content is 0.5～5%.
The operation blending process is: each component is contained respectively in the vessel of preparing burden, and unification is placed in the vacuum drying oven and toasts then, and baking end back taking-up raw material are put into and carried out the premix processing in the ball mill.
Charging sequence is: LiMn2O4 → gas phase SiO
2Or AL
2O
3, grind, add conductive agent again, continue to grind.When grinding, begin to prepare bonding agent, solvent is added in the Vacuum mixer, then the bonding agent that measures is joined wherein stir process.The raw material that all mixing are finished are transferred to stir process in the vacuum stirring equipment that prepares bonding slurry with the batching vessel then, eliminate bubble after stirring finishes and handle.Make anode with coating machine at last.
The quality proportioning of negative pole material is: negative electrode active material graphite 75%～96%, and conductive agent: 0.5～15%, thickener: 0.5～15%, aqueous adhesive: 2.5%～15%.Each component sum is 100%.
The operation blending process is: take by weighing each component and contain respectively in the batching vessel.Water is put into vacuum stirring equipment, then thickener that measured and aqueous adhesive are added wherein to stir process.Bonding agent stirs and finishes, and conductive agent that measured and graphite is joined in the charging basket again, and stir process is eliminated bubble after stirring finishes and handled.Be coated on the Copper Foil as battery cathode with coating machine at last.
The positive/negative plate back that completes is carried out welding electrode ear, encapsulation, fluid injection, step such as is changed into and finally make the finished product battery pack by existing conventional method.Concrete technological process sees Fig. 3 for details.
Battery protection circuit aspect externally, the present invention carries out the batch (-type) float management by lithium battery group management system BMS (BtteryManagement Systerm) to battery, has avoided battery to be in the constant voltage floating charge for a long time, the harm that battery life is brought.Concrete batch (-type) float management is: the preparation of manganate lithium ion battery group is finished and is carried out constant current-constant voltage (CC-CV) charging process, enter the open circuit static condition by BMS control then, (X is 75～99 when capacity is reduced to the X% of batteries charging deboost initial capacity, preferred 80～85), reenter additional electricity condition by BMS control, after finishing, additional electricity enters the open circuit static condition again, according to this circulation; Wherein said additional electricity condition adopts constant current-constant voltage (CC-CV) two-part charging method.
After the work of manganate lithium ion battery group power backup, again carry out constant current-constant voltage charge process, enter the open circuit static condition by BMS control then, (X is 75～99 when capacity is reduced to the X% of batteries charging deboost initial capacity, preferred 80～85), reenter additional electricity condition by BMS control, enter the open circuit static condition again after additional electricity is finished, according to this circulation.Replenish electric process and battery pack to be carried out the CC-CV charging process identical.Concrete batch (-type) float management process sees Fig. 2 for details.
The present invention is in the inside battery configuration aspects, by to lithium manganate battery in the process of making anode sizing agent, add 0.5～15% aerosil (SiO
2) or alundum (Al (AL
2O
3) material, these materials have bigger specific area, can powerfully reunite, be coated on the surface of anodal lithium manganate material, these sorptive materials can form a kind of gel state under the effect of the bonding agent (PVDF) of electrolyte and electrode simultaneously, easier surface attached to electrode has strengthened the stability of electrode coating layer.These two kinds of materials all are the electromagnetic type materials in addition, can not affect greatly the electric conductivity of electrode, thereby the electrical property to battery do not impact when playing support electrode surface skeleton function.On the basis in conjunction with the inside battery structure of modification, the present invention adopts the batch (-type) float management, thereby has avoided to greatest extent that battery is long-term to load a constant voltage, the harm that battery is caused.The synergy that the method that this internal structure changes and external circuit control combines produces, make the inside battery structure more stable, reduced the incidence of shortcomings such as inside battery electrolyte decomposition, aerogenesis simultaneously, strengthen floating resistance of lithium manganate lithium ion battery system, greatly improved the cycle life of battery.
Description of drawings
Fig. 1 is the anti-floating charge test loop of the battery product comparison diagram of embodiment 1 and Comparative Examples 1.
1# is embodiment 1 among the figure, and 2# is embodiment 2.
Fig. 2 is a battery pack batch (-type) management of charging and discharging schematic diagram.
Among the figure, T1 and T3 process are charging process, are constant current-constant voltage (CC-CV) mode; T1 is the charging process of BMS control; T3 is the additional electric process of BMS control; T2 is that the lithium battery group open circuit of BMS control leaves standstill process; T4 is the backup module power backup course of work.
Fig. 3 is a manganate lithium ion battery preparation flow schematic diagram.
Embodiment
Anodal blending process takes by weighing the LiMn2O4 of 850g with electronic balance, takes by weighing the conductive agent SP of 30g, takes by weighing the gas phase SiO of 50g
2Take by weighing the bonding agent PVDF of 50g, contain respectively in the batching vessel, unified then being placed in the vacuum drying oven, oven temperature is set: 80～120 ℃, stoving time: 12～24h, baking waits until that oven temperature is reduced to 50 ℃ after finishing, the taking-up raw material are put into and are carried out the premix processing in the ball mill.
Charging sequence is: first LiMn2O4, back gas phase SiO
2, grinding 2～6h, material ball ratio is 1: 1, adds SP again, continues to grind 2～6h.
When grinding, begin to prepare bonding agent, the nmp solvent of 600g is added in the Vacuum mixer of 5L, then the PVDF that measures is joined wherein, carry out the stir process of 5～10h with the rotating speed of 30HZ.The raw material that all mixing are finished are transferred to the batching vessel then, the 5L that has prepared the PVDF slurry vacuumizes in the mixing plant, carry out the stir process of 5～10h again with the rotating speed of 20HZ, stir to finish usefulness-0.075MPa～-vacuum degree of 0.085MPa keeps vacuum 30min to eliminate the bubble processing.Use the laboratory coating machine at last, be coated to uniformly on the 20 μ m aluminium foils as anode by The tape casting.
The cathode blending process takes by weighing the graphite of 850g with electronic balance, takes by weighing the conductive agent SP of 50g, takes by weighing the thickener CMC of 50g, takes by weighing the aqueous adhesive LA-132 of 50g, contains respectively in the batching vessel.
1000g water is put into 5L vacuumize in the mixing plant, then CMC that measured and LA-132 aqueous adhesive are added to wherein, the rotating speed that 30HZ is set carries out the stir process of 1～2h.
Bonding agent stirs and to finish, and SP that measure and graphite is joined in the 5L charging basket again, and the rotating speed that 20HZ is set carries out the stir process of 5～10h, stir finish usefulness-0.075MPa～-the vacuum degree maintenance vacuum 30min of 0.085MPa eliminates the bubble processing.Use the laboratory coating machine at last, be coated to uniformly on the 9 μ m Copper Foils as battery cathode by The tape casting.
Prepare the 12Ah manganate lithium ion battery according to Fig. 3 method.Carry out the floating charge experiment after the cell preparation, concrete steps are: constant current 8A charges to 4.2V, and battery maintains 4.2V, keeps this voltage 48h, and then carries out the 8A discharge, and repetition cycle of discharging and recharging of aforesaid operations is a cycle period, repeats 125 cycles.The results are shown in Figure 1.
At outside batteries lithium battery group management system BMS is set battery is carried out the batch (-type) float management, concrete batch (-type) float management is: the manganate lithium ion battery group carries out entering the open circuit static condition by BMS control behind constant current-constant voltage charge, when capacity is reduced to the X% of batteries charging deboost initial capacity (X is 85), reenter CC-CV by BMS control and replenish electricity condition, after finishing, additional electricity enters the open circuit static condition again, according to this circulation.To the work of manganate lithium ion battery group power backup, again carry out constant current-constant voltage charge process, enter the open circuit static condition by BMS control then, when capacity is reduced to the X% of batteries charging deboost initial capacity (X is 85), reenter additional electricity condition by BMS control, after finishing, additional electricity enters the open circuit static condition again, according to this circulation.
This manganate lithium ion battery system applies is used under online normal standby of base station communication or running status, and system's operation is normal.Long-play shows, battery recycles the life-span and obviously is better than existing conventional batteries.
Comparative Examples 1
Battery does not add gas phase SiO in the preparation in anodal material
2, other preparation methods are with embodiment 1.Carry out the floating charge experiment according to the method for embodiment 1 after the cell preparation.The results are shown in Figure 1.From the visible battery of the present invention of result existing battery on anti-floating charge ability bigger enhancing is arranged.
This routine battery is applied to embodiment 1 same area under the situation that does not adopt BMS and batch (-type) float management, long-play shows that this routine battery recycles the life-span than embodiment low 30%.
Anodal blending process takes by weighing the LiMn2O4 of 900g with electronic balance, takes by weighing the conductive agent SP of 40g, takes by weighing the Al of 40g
2O
3Take by weighing the bonding agent PVDF of 40g, contain respectively in the batching vessel, unified then being placed in the vacuum drying oven, oven temperature is set: 80～120 ℃, stoving time: 12～24h, baking waits until that oven temperature is reduced to 50 ℃ after finishing, the taking-up raw material are put into and are carried out the premix processing in the ball mill.
Charging sequence is: first LiMn2O4, back AL
2O
3, grinding 2～6h, material ball ratio is 1: 1, adds SP again, continues to grind 2～6h.
When grinding, begin to prepare bonding agent, the nmp solvent of 700g is added in the Vacuum mixer of 5L, then the PVDF that measures is joined wherein, carry out the stir process of 5～10h with the rotating speed of 30HZ.The raw material that all mixing are finished are transferred to the batching vessel then, the 5L that has prepared the PVDF slurry vacuumizes in the mixing plant, carry out the stir process of 5～10h again with the rotating speed of 20HZ, stir to finish usefulness-0.075MPa～-vacuum degree of 0.085MPa keeps vacuum 30min to eliminate the bubble processing.Use the laboratory coating machine at last, be coated to uniformly on the 20 μ m aluminium foils as anode by The tape casting.
The cathode blending process takes by weighing the graphite of 910g with electronic balance, takes by weighing the conductive agent SP of 40g, takes by weighing the thickener CMC of 40g, takes by weighing the aqueous adhesive LA-132 of 60g, contains respectively in the batching vessel.
1000g water is put into 5L vacuumize in the mixing plant, then CMC that measured and LA-132 aqueous adhesive are added to wherein, the rotating speed that 30HZ is set carries out the stir process of 1～2h.
Bonding agent stirs and to finish, and SP that measure and graphite is joined in the 5L charging basket again, and the rotating speed that 20HZ is set carries out the stir process of 5～10h, stir finish usefulness-0.075MPa～-the vacuum degree maintenance vacuum 30min of 0.085MPa eliminates the bubble processing.Use the laboratory coating machine at last, be coated to uniformly on the 9 μ m Copper Foils as battery cathode by The tape casting.
Prepare the 12Ah manganate lithium ion battery according to Fig. 3 method.Carry out the floating charge experiment after the cell preparation, concrete steps are: constant current 8A charges to 4.2V, and battery maintains 4.2V, keep this voltage 48h, and then carry out the 8A discharge, repetition cycle of discharging and recharging of aforesaid operations is a cycle period, repeat 125 cycles, capability retention is 97.83%.
At outside batteries lithium battery group management system BMS is set battery is carried out the batch (-type) float management, concrete batch (-type) float management is: the manganate lithium ion battery group carries out entering the open circuit static condition by BMS control behind constant current-constant voltage charge, when capacity is reduced to the X% of batteries charging deboost initial capacity (X is 85), reenter CC-CV by BMS control and replenish electricity condition, after finishing, additional electricity enters the open circuit static condition again, according to this circulation.To the work of manganate lithium ion battery group power backup, again carry out constant current-constant voltage charge process, enter the open circuit static condition by BMS control then, when capacity is reduced to the X% of batteries charging deboost initial capacity (X is 85), reenter additional electricity condition by BMS control, after finishing, additional electricity enters the open circuit static condition again, according to this circulation.
This manganate lithium ion battery system applies is used under online normal standby of base station communication or running status, and system's operation is normal.Long-play shows, battery recycles the life-span and obviously is better than existing conventional batteries.
Comparative Examples 2
Add AL in the not anodal in the preparation material of battery
2O
3, other preparation methods are with embodiment 2.Carry out the floating charge experiment according to the method for embodiment 2 after the cell preparation.Repeat 125 cycles, capability retention is 92.97%.
This routine battery is applied to embodiment 2 same area under the situation that does not adopt BMS and batch (-type) float management, long-play shows that this routine battery recycles the life-span than embodiment low 32%.
Embodiment 3
The system of Application Example 1 in communication lithium manganate battery system.Consider from whole system, batch (-type) floating charge design, normal holding state power consumption: under the normal holding state of battery system, " RUN " lamp (LED lamp) flicker power consumption electric current 2～3mA, battery power consumption is under this state:
| Preparation time | 5 |
10 days | 15 |
20 days | 25 |
30 days |
| The LED lamp | ??0.36Ah | ??0.72Ah | ??1.08Ah | ??1.44Ah | ??1.80Ah | ??2.16Ah |
| Self-discharge of battery | ??0.03Ah | ??0.06Ah | ??0.09Ah | ??0.12Ah | ??0.15Ah | ??0.18Ah |
| Accumulative total | ??0.39Ah | ??0.78Ah | ??1.17Ah | ??1.56Ah | ??1.95Ah | ??2.34Ah |
| Residual capacity | ??11.61Ah | ??11.22Ah | ??10.83Ah | ??10.44Ah | ??10.05Ah | ??9.66Ah |
| Rated capacity % | ??96.8％ | ??93.5％ | ??90.3％ | ??87.0％ | ??83.8％ | ??80.5％ |
Test by the above-mentioned capacity power consumption accumulative total of shelving, for 12Ah type communication lithium manganate battery system, when the online power backup of battery system uses, the capacity of battery drops to about 85% of rated capacity, probably open charging again 1 month time, to no longer be continuous and constant pressure floating charge on the complete meaning, battery system will regularly discharge and recharge in this state, the power backup process of system has become a kind of shallow shallow operating state of putting of filling, and the batch (-type) float management by BMS is guaranteed the life-span of battery preferably.
Claims (6)
1. method that improves floating resistance of lithium manganate lithium ion battery system, comprise the preparation of manganate lithium ion battery and the control of outside batteries protective circuit, it is characterized in that when manganate lithium ion battery prepares the adding mass content is 0.5～15% aerosil or alundum (Al in anodal material; After the preparation of manganate lithium ion battery group is finished,, battery is carried out the batch (-type) float management at battery pack outer setting lithium battery group management system.
2. the method for raising floating resistance of lithium manganate lithium ion battery system according to claim 1, it is characterized in that described batch (-type) float management is: carry out constant current-constant voltage charge process earlier after the preparation of manganate lithium ion battery group is finished, enter the open circuit static condition by the control of lithium battery group management system then, be reduced to 75～99% o'clock of batteries charging deboost initial capacity until capacity, reenter additional electricity condition by the control of lithium battery group management system, after finishing, additional electricity enters the open circuit static condition again, according to this circulation; Wherein said additional electricity condition adopts constant current-constant voltage two-part charging method.
3. the method for raising floating resistance of lithium manganate lithium ion battery system according to claim 2, after it is characterized in that the work of manganate lithium ion battery group power backup, again carry out constant current-constant voltage charge process, enter the open circuit static condition by the control of lithium battery group management system then, be reduced to 75～99% o'clock of batteries charging deboost initial capacity until capacity, reenter additional electricity condition by the control of lithium battery group management system, after finishing, additional electricity enters the open circuit static condition again, according to this circulation.
4. according to the method for claim 2 or 3 described raising floating resistance of lithium manganate lithium ion battery system, it is characterized in that the manganate lithium ion battery group enters open circuit static condition to capacity and is reduced to 80～85% of batteries charging deboost initial capacity and reenters additional electricity condition.
5. the method for raising floating resistance of lithium manganate lithium ion battery system according to claim 1, the mass content that it is characterized in that described anodal each component of material is a positive active material LiMn2O4 75%～96%, conductive agent 0.5～15%, structural stabilizing agent 0.5～15%, bonding agent 2.5%～15%, each component sum is 100%; Wherein said structural stabilizing agent is aerosil or alundum (Al.
6. improve the method for floating resistance of lithium manganate lithium ion battery system according to claim 1 or 5, it is characterized in that the mass content of aerosil in the anodal material or alundum (Al is 0.5～5%.
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| CN103594750A (en) * | 2013-11-22 | 2014-02-19 | 上海航天电源技术有限责任公司 | Floating charge resistant lithium ion battery module and floating charge method thereof |
| CN112386169A (en) * | 2019-08-19 | 2021-02-23 | 深圳市宝乐智能机器有限公司 | Cleaning robot, method of controlling the same, and computer-readable storage medium |
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| CN1988317A (en) * | 2005-12-21 | 2007-06-27 | 刘孝伟 | Self adaptive fixed flow intermittent pulse limit time charging method |
| CN1834023A (en) * | 2006-02-27 | 2006-09-20 | 北京中润恒动电池有限公司 | Compsns contg. additive of stable spinel-type lithium manganate anode sheet and prepn. process |
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| CN103594750A (en) * | 2013-11-22 | 2014-02-19 | 上海航天电源技术有限责任公司 | Floating charge resistant lithium ion battery module and floating charge method thereof |
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Application publication date: 20101027 |