CN100483801C - Technology for preparing anode of lithium polymer battery - Google Patents

Technology for preparing anode of lithium polymer battery Download PDF

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CN100483801C
CN100483801C CNB021250790A CN02125079A CN100483801C CN 100483801 C CN100483801 C CN 100483801C CN B021250790 A CNB021250790 A CN B021250790A CN 02125079 A CN02125079 A CN 02125079A CN 100483801 C CN100483801 C CN 100483801C
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黄穗阳
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Abstract

The invention provides a process for preparing positive electrode based on the characteristic of the lithium polymer battery arrangement featuring using various kinds of lithium embedded oxide combined or mixed together as the active material of the positive electrode, wherein these physical mixing member includes the two element system and three element system. The positive electrode prepared by the process of the invention can enable the lithium polymer battery to provide higher power density and more safe performance. The positive electrode making process provide by the invention is also adapted for the lithium ion battery products.

Description

The technology of preparing of anode of lithium polymer battery
The present invention relates to most important element in the lithium polymer battery--the technology of preparing of positive electrode.
Although lithium polymer battery is the upgraded product of lithium ion battery. lithium ion battery remains the main force's power supply on the global mobile phone market at present, but, renewal and development along with technology, OEM and cellphone subscriber have higher requirement to battery, for example thinner, lighter, arbitrary shape, more high-energy-density, safer and low price more.Lithium ion battery not only all can not meet the demands aspect thin, light, arbitrary shape and the energy density.And, because use inflammable in the lithium ion battery and corrosive liquids as electrolyte, its security performance makes mobile phone production firm and user worry always.Battery leakage causes the accident of electronic device corrosion and damage also to happen occasionally.In addition, the manufacturing process complexity of lithium ion battery, cost height, price are expensive, for example, need to use expensive laser-beam welding machine sealing-in battery case.Therefore, it is imperative to research and develop battery of new generation.
The Battery Company of industrial flourishing state such as the U.S. rose since 1994 and begins to research and develop polymer Li-ion battery, for example the Samsung of the wealthy company of U.S. young tiger (BellCommunication Research Inc.), long-lived Battery Company (Ultralife Battery Inc.), fear Lun Si company (Valence TechnologyInc.), Korea S and the companies such as Hitachi of Japan successively declare in patent, have invented polymer Li-ion battery.Such battery adopts the substrate of wire netting (or metal forming) as electrode, electrode film is coated on the wire netting, solid polymer electrolyte has replaced liquid electrolyte, and stacked battery core has replaced the coiled battery core, and the compound soft wrapping of aluminium pool/plastics has replaced metal (aluminium or steel) shell.The advantage of this type of polymer Li-ion battery is that the overall dimensions variation is easy and easy, can order according to user's degree of requirement body and make battery, and is more favourable for the super book type battery below the 2mm.
But the positive electrode prescription of this type of polymer Li-ion battery nearly all is to plagiarize from the positive electrode prescription of older generation's lithium ion battery, and promptly the active material of positive electrode remains lithium and cobalt oxides (LiCoO 2), the also few of change of the rerum natura of other non-active material and proportioning.Although housing material has replaced metal (stainless steel or aluminium) shell by aluminium pool/composite plastic film soft wrapping, make volume and weight that minimizing all be arranged slightly, but, because positive electrode prescription composition does not change, active material is wherein also indiscriminately imitated motionless, therefore, the energy density per unit volume metric density of the energy density per unit volume metric density of this type of polymer Li-ion battery and gravimetric specific energy density and older generation's lithium ion battery and gravimetric specific energy density are close.Technical performance under the room temperature, how much superior polymer Li-ion battery is unlike lithium ion battery.On the contrary, because electrolyte is solid-state or solid-liquid two phase systems, internal resistance increases, and at aspects such as low temperature discharge, room temperature high current charge-discharges, polymer Li-ion battery is on the contrary not as lithium ion battery.Therefore, the technical performance of polymer Li-ion battery needs to improve.
Positive electrode is of most critical in the various elements of lithium polymer battery, and it not only is related to the technical performance of battery product, and as discharge capacity, cycle life charges and discharge speed and low-temperature characteristics, and directly determines the quality of battery safety.In order to improve the technical performance of existing polymer Li-ion battery, keep its fail safe simultaneously again, it is vital using new technology to prepare positive electrode.Therefore, the purpose of this invention is to provide the positive electrode that a kind of new technology prepares colloidal state or solid-state lithium polymer battery.The polymer Li-ion battery that adopts process of the present invention to produce is compared with polymer Li-ion battery or liquid lithium ion battery that prior art is produced, has superenergy density, better security performance and lower production cost.
The characteristics of positive electrode technology of preparing provided by the invention are, use the characteristics and thinner, lighter, the more market demands of high-energy-density and flexible design of soft wrapping according to lithium polymer battery, the latest scientific research of positive electrode material is applied in the positive electrode preparation, strengthens positive reaction as far as possible and improve discharge energy density and reduce side reaction and reduce and fill the phenomenon that rises.This technology of preparing comprises component prescription, production technology and the method for testing of positive electrode.
Below at first the research and development historical background of positive electrode material is done general introduction, then positive electrode technology of preparing provided by the present invention is done detailed description, comprising component prescription, production technology and method of testing.Positive electrode technology of preparing provided by the present invention is not only applicable to the polymer Li-ion battery production process, and can be applied to the lithium ion battery product.
There is the collection of lithium ion to go out and inserts the embedding effect since U.S. professor J.Googenough in 1974 has found three kinds of otide containing lighium things, can be as the positive electrode of lithium battery, and after obtaining multinomial patent with this, in decades, there is thousands of scientist to try to find out in the world or synthetic new positive electrode.But, lithium and cobalt oxides (LiCoO 2), lithium nickel oxide (LiNiO 2) and lithium manganese oxide (LiMn 2O 4) lithium of these three kinds of early detections inserts the main material that the embedding oxide remains current lithium battery anode.The new material of finding or synthesizing is in energy density, and everyways such as electrochemical stability performance and production cost are inserted the embedding oxide not as three kinds of lithiums of above-mentioned early detection.
The setback that is met with in discovery and synthon field of new impels the various countries scientist to turn to the synthetic solid solution of inserting the embedding oxide based on above-mentioned three kinds of lithiums.In recent years, there is multiple solid solution to be developed success, and batch process is arranged based on lithium, cobalt, nickel and manganese oxygen five elements.Compare with the monomer oxide, solid solution, oxide has the characteristics of high discharge capacity, low-voltage curve and low stability.The main chemical property and the exothermic reaction parameter of monomer and solid solution, oxide have been listed in the table 1.
See that from table 1 three kinds of lithiums of Fa Xianing are inserted in the embedding oxide in early days, lithium and cobalt oxides (LiCoO 2) being the most outstanding: its discharge capacity and security performance are all at lithium nickel oxide (LiNiO 2) and lithium manganese oxide (LiMn 2O 4) between.Because lithium manganese oxide (LiMn 2O 4) be the three-dimensional channel structure, can disengage whole lithium ions and not recurring structure collapse.Overcharge with condition such as overheated under, its exothermic heat of reaction is minimum, is safest in all positive electrodes at present.Lithium nickel oxide (LiNiO 2) allow to disengage 75 moles of % lithium ions, can reach the highest discharge capacity in all positive electrodes, but because of its layer structure less stable, overcharge with condition such as overheated under, recurring structure collapse easily, and discharge a large amount of oxygen, served as the fuel of aggravation exothermic heat of reaction, make it become the most dangerous positive electrode.Overcharge with condition such as overheated under, lithium nickel oxide (LiNiO 2) exothermic reaction is:
The electrochemistry of table 1, various monomer and solid solution, oxide and thermal response parameter
Sequence number Title Molecular formula Crystal structure Discharge capacity (mAh/g) Charging capacity (mAh/g) Put and fill efficient (%) Maximum potential (V) Initial temperature (℃) Exothermic heat of reaction (J/g)
1 Lithium and cobalt oxides LiCoO 2 α-NaFeO 2 140 146 95.9 4.30 250 610
2 Lithium nickel oxide LiNiO 2 α-NaFeO 2 204 231 88.3 4.20 220 1670
3 Lithium manganese oxide LiMn 2O 4 Cubic spinel 128 142 90.1 4.45 260 174
4 Lithium manganese oxide LiMnO 2 Stratiform 210 245 85.7 4.00 - -
5 Lithium-cobalt-nickel oxide LiCo 0.2Ni xAl yO 2 (x＝0.8，y＝0) α-NaFeO 2 194 212 91.5 4.20 235 1400
6 Lithium-cobalt-nickel oxide LiCo 0.2Ni xAl yO 2 (x＝0.77，y＝0.03) α-NaFeO 2 189 208 90.9 4.25 242 950
7 Lithium-cobalt-nickel oxide LiCo 0.2Ni xAl yO 2(x＝0.75，y＝0.05) α-NaFeO 2 179 199 89.9 4.25 248 760
8 Lithium-cobalt-nickel oxide LiCo 0.2Ni xMg yO 2 (x＝0.77，y＝0.03) α-NaFeO 2 178 197 90.4 4.25 1105
9 Lithium-cobalt-nickel oxide LiCo 0.2Ni xTi yO 2 (x＝0.77，y＝0.03) α-NaFeO 2 176 199 88.4 4.25 240 1040
10 The lithium, cobalt, nickel and manganese oxide Li αCo βNi γMn δO 2 (α＝δ＝0.67，β＝0，γ＝0.33) Stratiform 174 * 193 * 90.2 4.5 - -
11 The lithium, cobalt, nickel and manganese oxide Li αCo βNi γMn δO 2 (a＝δ＝0.67，β＝0.33，γ＝0) Stratiform 166 * 178 * 93.3 4.5 - -
12 The lithium, cobalt, nickel and manganese oxide Li αCo βNi γMn δO 2 (α＝δ＝0.67，β＝0.04，γ＝0.30) Stratiform 185 * 193 * 95.9 4.5 - -
13 The lithium, cobalt, nickel and manganese oxide Li αCo βNi γMn δO 2 (α＝δ＝0.67，β＝0.08，γ＝0.26) Stratiform 172 * 178 * 96.6 4.5 - -
Annotate: except that indicating especially, charging capacity and discharge capacity are all charging for the first time and discharge, are to electrode with the lithium metal.Maximum potential is to end voltage with the lithium metal for the half-cell to electrode allows the knot of safe charging.When initial temperature is to use heat difference scanner specimen, the slope of exothermic heat of reaction curve start-up portion and the intersection point temperature of background baseline.The condition that specimen material overcharges is: positive pole is packed into the lithium metal in the half-cell to electrode, charge to and allow the knot of safe charging to end voltage, then constant voltage 16 hours under this voltage.Exothermic heat of reaction is the integration of sample exothermic peak area.
* charging capacity and discharge capacity are all charging for the second time and discharge, are to electrode with the lithium metal.In this type of solid solution, oxide, Li +Have vacant position in the position, through charging for the first time, from electrode lithium metal is obtained to replenish there.
Lithium and cobalt oxides (LiCoO 2) Co-O layer in the structure is stronger to the lithium ion binding force that is positioned at interlayer, allows to disengage lithium ion and has only 55 moles of %, its discharge capacity is than (LiNiO 2) low, but than lithium manganese oxide (LiMn 2O 4) high by 21%.And its layer structure stability is better, overcharge with condition such as overheated under, be not easy the recurring structure collapse.Even structural collapse has taken place, the amount of oxygen that discharges is also less, therefore, takes all factors into consideration lithium and cobalt oxides (LiCoO from discharge capacity, security performance and other factors 2) once be the optimal selection of anode material of lithium battery.
In the lithium, cobalt, nickel and manganese oxygen solid solution of various chemical syntheses, LiCo 0.2Ni 0.8-xAl xO 2(x=0～0.05) is the most outstanding and the most ripe solid solution, oxide.Its advantage is, at LiCoO 2The middle nickel element that adds is replaced cobalt element, makes LiCo 0.2Ni 0.8-xAl xO 2The discharge capacity of solid solution, oxide and LiNiO 2The monomer oxide is close.And cobalt and aluminium ion are at LiCo 0.2Ni 0.8-xAl xO 2Played the effect of crystal structure strengthening agent in the solid solution, oxide, not only made the charge and discharge circulation life of this solid solution, oxide compare LiNiO 2The monomer oxide is superior many, and overcharge with condition such as overheated under the exothermic heat of reaction amount significantly reduce (seeing Table 1).In addition, because the nickel metal is more cheap than cobalt raw metal, and LiCo 0.2Ni 0.8-xAl xO 2The production technology of solid solution, oxide and LiCoO 2The monomer oxide is similar.Therefore, this solid solution, oxide production cost is lower.
Use LiCo 0.2Ni 0.8-xAl xO 2Solid solution, oxide is the discharge inferior quality of battery as one of shortcoming of lithium polymer battery positive electrode.The discharge quality of battery is to be characterized by two major parameters, first discharge mid-point voltage (voltage during discharge capacity 50%), and it two is discharge characteristic curves.In following analysis description and diagram, can see LiCo0. 2Ni 0.8-xAl xO 2The discharge mid-point voltage of solid solution, oxide compares LiCoO 2The monomer oxide is low, but compares LiNiO 2Monomer oxidation object height; The discharge characteristic curve of this solid solution, oxide is an oblique line that descends continuously, with LiNiO 2The discharge characteristic curve of monomer oxide is similar.
LiCo 0.2Ni 0.8-xAl xO 2Two of the shortcoming of solid solution, oxide is that charge and discharge circulation life and security performance are not so good as LiCoO 2The monomer oxide is good.As previously mentioned, LiCo 0.2Ni 0.8-xAl xO 2Solid solution, oxide is LiCoO 2And LiNiO 2The compound of two kinds of monomer oxides, and be rich ni solid solution.Therefore, it not only has the characteristic of two kinds of monomer oxides concurrently, and the more close LiNiO of its characteristic 2The monomer oxide.Cycle life and security performance all interrelate with the crystal structural stability of solid solution.According to " on-the-spot X-light " research, repeated charge be the collection of lithium ion go out with insertion process in, crystal structure has～6% expansion and contraction.Because LiCo 0.2Ni 0.8-xAl xO 2The crystal structure of solid solution, oxide is looser, this expand repeatedly and contraction can cause crystal structure to change gradually, charge-discharge characteristic variation, cycle life decay.By the same token, LiCo 0.2Ni 0.8-xAl xO 2Solid solution, oxide overcharge with condition such as overheated under reaction can emit more heat.
Positive electrode prescription design provided by the present invention will overcome the problems referred to above effectively, and the advantage of each type oxide is brought into play.According to the characteristics of the polymer dielectric of lithium polymer battery and flexible package and thinner, lighter, the more market demands of high-energy-density and flexible design, the present invention proposes with physical admixture, design the positive pole of battery according to user's actual needs, reasonably all kinds of lithiums are inserted the embedding combination of oxides and mixed and be used as active positive electrode material.
By the preparation method of reference accompanying drawing and detailed description anode of lithium polymer battery of the present invention, above-mentioned purpose of the present invention and advantage will be apparent, wherein:
Fig. 1 is the discharge characteristic curve that three kinds of lithiums of early detection are inserted the embedding oxide: lithium and cobalt oxides (LiCoO 2), lithium nickel oxide (LiNiO 2) and lithium manganese oxide (LiMn 2O 4).
Fig. 2 is the positive electrode discharge characteristic curve that designs and prepare by binary system prescription provided by the present invention, and with mix before two oxide discharge characteristic curves contrast.
Fig. 3 shows LiCoO 2/ LiCo 0.2Ni 0.8-xAl xO 2(x=0) in the binary system discharge capacity and exothermic heat of reaction with LiCo 0.2Ni 0.8-xAl xO 2(x=0) variation of mixed volume.
Fig. 4 is the positive electrode discharge characteristic curve that designs and prepare by ternary system prescription provided by the present invention, and with mix before three oxide discharge characteristic curves contrast.
Fig. 5 shows LiCoO 2/ LiMn 2O 4/ LiCo 0.2Ni 0.75Al 0.05O 2Discharge capacity and exothermic heat of reaction are with LiMn in the ternary system 2O 4/ LiCo 0.2Ni 0.75Al 0.05O 2The variation of mixed volume.
With reference to the accompanying drawings, use list data and most preferred embodiment to explain component prescription of the present invention, preparation technology and method of testing.
One, component prescription
Comprise active and non-active material two major parts in the anodal composition, and active material is crucial.Fig. 1 has shown with lithium and cobalt oxides (LiCoO 2), lithium nickel oxide (LiNiO 2) and lithium manganese oxide (LiMn 2O 4) three kinds of conventional positive electrode active materials make the discharge voltage indicatrix that positive electrode and lithium paper tinsel are the half-cell that constitutes of negative electrode respectively, other relevant concrete parameter sees Table 1.Mn oxide (LiMn 2O 4) have the highest mid point discharge voltage, and lithium nickel oxide (LiNiO 2) the mid point discharge voltage minimum, particularly in the discharge middle and later periods, it is too fast that the discharge voltage indicatrix descends, and may influence the characteristic of power device.
Fig. 2 shows LiCo 0.2Ni 0.8-xAl xO 2The discharge characteristic curve of solid solution, oxide.The discharge mid-point voltage of this solid solution, oxide compares LiCoO 2Monomer oxide low 5%.But, visible LiCo from table 1 0.2Ni 0.8-xAl xO 2The discharge capacity of (x=0～0.05) solid solution, oxide compares LiCoO 2Monomer oxidation object height goes out 28-39%.Because being the discharge mid-point voltage, energy density multiply by discharge capacity, therefore, and LiCo 0.2Ni 0.8-xAl xO 2The discharge energy density of (x=0～0.05) solid solution, oxide still surpasses LiCoO 2Monomer oxide 23～34%.
Design and prepare the positive electrode of lithium polymer battery by prescription provided by the present invention, its energy density, discharge quality, cycle life and security performance all have bigger improvement.Basic recipe provided by the present invention is designed to 89% active material+4% conductive carbon powder+7% polymer-binder.As previously mentioned, active material is the key component of positive electrode prescription.Below this part is made detailed description, and provide most preferred embodiment of the present invention.
Example one: LiCoO 2/ LiCo 0.2Ni 0.8Al 0.0O 2Binary system
In sum, LiCoO 2And LiCo 0.2Ni 0.8Al 0.0O 2Be respectively the preferred material in monomer oxide and the solid solution, oxide, but the two all have its shortcoming.If the two is combined, can learn from other's strong points to offset one's weaknesses mutually.Electrochemistry and the exothermic heat of reaction parameter of one of this binary system (x=0 series) have been listed in the table 2.With L iCo 0.2Ni 0.8Al 0.0O 2Solid solution, oxide is with physics mode and LiCoO 2The monomer oxide mixes the capacity of back charge and discharge all with LiCo 0.2Ni 0.8Al 0.0O 2The increase of solid solution, oxide and strengthening the highlyest is increased to 39%.Meanwhile, exothermic heat of reaction also increases to some extent, and its amplification is up to 130%.This LiCoO 2/ LiCo 0.2Ni 0.8Al 0.0O 2Blending ingredients is that the discharge characteristic curve of A:B=50:50 is seen Fig. 2 in the binary system.See that from figure the discharge characteristic curve of this binary mixed system is at discharge initial stage (0～46%) and LiCoO 2Discharge characteristic curve overlaid.And in the discharge later stage (54～100%), the discharge characteristic curve of binary system is to LiCo 0.2Ni 0.8Al 0.0O 2The discharge characteristic curve close.This explanation is in the high potential district, with LiCoO 2Discharge be main, and in the electronegative potential district, then with LiCo 0.2Ni 0.8Al 0.0O 2Discharge be main.And discharge mid-point voltage and LiCoO 2Mid-point voltage be close.Therefore, LiCoO 2/ LiCo 0.2Ni 0.8Al 0.0O 2Binary mixed system has following two advantages: compare LiCoO 2Exceed 19% energy density and compare LiCo 0.2Ni 0.8Al 0.0O 2Superior discharge characteristic curve.
Table 2 LiCoO 2: LiCo 0.2Ni 0.8Al 0.0O 2=A:B electrochemistry and heat release parameter
Sequence number The A:B mixing ratio Discharge capacity (mAh/g) Charging capacity (mAh/g) Charge and discharge efficient (%) Exothermic heat of reaction (J/g) Discharge capacity increases (%) Exothermic heat of reaction increases (%)
0 100:0 140 146 95.9 610 0 0
1 80:20 151 159 94.7 768 8 26
2 60:40 162 172 93.7 926 15 52
3 50:50 167 179 93.3 1005 19 65
4 40:60 172 186 92.9 1084 23 78
5 20:80 183 199 92.2 1242 31 104
6 0:100 194 212 91.5 1400 39 130
Fig. 3 shows LiCoO 2/ LiCo 0.2Ni 0.8Al 0.0O 2The discharge capacity of binary system and exothermic heat of reaction are with LiCo 0.2Ni 0.8Al 0.0O 2The increase of solid solution, oxide and increasing linearly.This is because LiCoO 2And LiCo 0.2Ni 0.8Al 0.0O 2Two kinds of materials mix with physics mode, do not have chemical reaction between the two, and the electrochemistry of its binary system and exothermic heat of reaction have additivity to the variation response of forming.The exothermic heat of reaction of binary system is with LiCo 0.2Ni 0.8Al 0.0O 2The speed ratio discharge capacity of the increase of solid solution, oxide is fast.
Example two: LiCoO 2/ LiCo 0.2Ni 0.77Al 0.03O 2Binary system
The electrochemistry and the exothermic heat of reaction parameter of another binary system (x=0.03 series) have been listed in the table 3.With LiCoO 2/ LiCo 0.2Ni 0.8Al 0.0O 2Binary mixed system is similar, with LiCo 0.2Ni 0.77Al 0.03O 2Solid solution, oxide is with physics mode and LiCoO 2After the monomer oxide mixed, the capacity of its charge and discharge was all with LiCo 0.2Ni 0.77Al 0.03O 2The increase of solid solution, oxide and strengthening, but the high-amplitude that increases is slightly smaller, reaches 35%.The advantage of this binary system is that the growth of exothermic heat of reaction greatly reduces, and the highest have only 56%.
Table 3 LiCoO 2: LiCo 0.2Ni 0.77Al 0.03O 2=A:B electrochemistry and heat release parameter
Sequence number The A:B mixing ratio Discharge capacity (mAh/g) Charging capacity (mAh/g) Put and fill efficient (%) Exothermic heat of reaction (J/g) Discharge capacity increases (%) Exothermic heat of reaction increases (%)
0 100:0 140 146 95.9 610 0 0
1 80:20 150 158 94.6 678 7 11
2 60:40 160 171 93.4 746 14 22
3 50:50 165 177 92.9 780 18 28
4 40:60 169 183 92.5 814 21 33
5 20:80 179 196 91.6 882 28 45
6 0:100 189 208 90.9 950 35 56
Example three: LiCoO 2/ LiCo 0.2Ni 0.75Al 0.05O 2Binary system
The electrochemistry and the exothermic heat of reaction parameter of the 3rd binary system (x=0.05 series) have been listed in the table 4.With two binary mixed systems in front Sihe difference is mutually arranged: with LiCo 0.2Ni 0.75Al 0.05O 2Solid solution, oxide is with physics mode and LiCoO 2After the monomer oxide mixed, the capacity of its charge and discharge was all with LiCo 0.2Ni 0.77Al 0.03O 2The increase of solid solution, oxide and strengthening, but the high-amplitude that increases is less, reaches 28%; And the rate of rise of exothermic heat of reaction is lower than the rate of rise of the capacity of discharge, and the highest have only 25%.Therefore, at three LiCoO 2/ LiCo 0.2Ni 0.8-xAl xO 2In (x=0,0.03,0.05) binary system, this binary system has been obtained between technical performance index and the safe performance indexes balance preferably, is the optimal selection of binary system.
Table 4 LiCoO 2: LiCo 0.2Ni 0.8-xAl xO 2(x=0.05)=A:B electrochemistry and heat release parameter
Sequence number The A:B mixing ratio Discharge capacity (mAh/g) Charging capacity (mAh/g) Put and fill efficient (%) Exothermic heat of reaction (J/g) Discharge capacity increases (%) Exothermic heat of reaction increases (%)
0 100:0 140 146 95.9 610 0 0
1 80:20 148 157 94.4 640 6 5
2 60:40 156 167 93.1 670 11 10
3 50:50 160 173 92.5 685 14 12
4 40:60 163 178 91.9 700 17 15
5 20:80 171 188 90.9 730 22 20
6 0:100 179 199 89.9 760 28 25
Example four: LiCoO 2/ LiMn 2O 4/ LiCo 0.2Ni 0.8Al 0.0O 2Ternary system
At LiCoO 2/ LiCo 0.2Ni 0.8-xAl xO 2Sneak into the 3rd composition lithium manganese oxide (LiMn in (x=0～0.05) binary system 2O 4), promptly form ternary system.The electrochemistry and the exothermic heat of reaction parameter of this ternary system have been listed in the table 5.At LiMn 2O 4/ LiCo 0.2Ni 0.8Al 0.0O 2Component ratio equity permanence condition under, LiCoO 2/ LiMn 2O 4/ LiCo 0.2Ni 0.8Al 0.0O 2Ternary system and LiCoO 2/ LiCo 0.2Ni 0.8Al 0.0O 2Binary system is similar: its discharge capacity and exothermic heat of reaction are all with LiCoO 2/ LiCo 0.2Ni 0.8Al 0.0O 2The increase of solid solution, oxide and increasing.
Table 5 LiCoO 2: LiMn 2O 4: LiCo 0.2Ni 0.8Al 0.0O 2=A:B:C
Ternary system electrochemistry and heat release parameter
Sequence number The A:B:C mixing ratio Discharge capacity (mAh/g) Charging capacity (mAh/g) Put and fill efficient (%) Exothermic heat of reaction (J/g) Discharge capacity increases (%) Exothermic heat of reaction increases (%)
0 100:0:0 140 146 95.9 610 0 0
1 80:10:10 144 152 94.8 645 3 6
2 60:20:20 148 158 93.8 681 6 12
3 40:30:30 152 164 92.9 716 9 17
4 20:40:40 156 170 92.0 752 12 23
5 0:50:50 161 176 91.2 787 15 29
Example five: LiCoO 2/ LiMn 2O 4/ LiCo 0.2Ni 0.77Al 0.03O 2Ternary system
The electrochemistry and the exothermic heat of reaction parameter of this ternary system have been listed in the table 6.It and LiCoO 2/ LiCo 0.2Ni 0.8Al 0.0O 2Binary system is obviously different, and its discharge capacity is with LiCoO 2/ LiCo 0.2Ni 0.8Al 0.0O 2The increase of solid solution, oxide and increasing, and exothermic heat of reaction reduces.The data of this ternary system show can accomplish to increase discharge capacity, and reduces exothermic heat of reaction simultaneously, and technical performance is taken into account mutually with security performance.
LiCoO 2/ LiMn 2O 4/ LiCo 0.2Ni 0.77Al 0.03O 2The blending ingredients of ternary system is that the discharge characteristic curve of A:B:C=20:40:40 is seen Fig. 4.See that from figure the discharge characteristic curve of this ternary hybrid system is at discharge initial stage (0～55%) and LiCoO 2And LiMn 2O 4The discharge characteristic curve mutually close.And in the discharge later stage (60～100%), the discharge characteristic curve of ternary system is to LiCo 0.2Ni 0.8Al 0.0O 2The discharge characteristic curve close.This explanation is in the high potential district, with LiCoO 2And LiMn 2O 4Discharge be main, and in the electronegative potential district, then with LiCo 0.2Ni 0.8Al 0.0O 2Discharge be main.The discharge mid-point voltage of ternary hybrid system is at LiCoO 2And LiMn 2O 4Mid-point voltage near.Therefore, this ternary hybrid system has following three advantages: (1) energy density is respectively than LiCoO 2And LiMn 2O 4Exceed 12% and 23% respectively; (2) discharge characteristic curve ratio LiCo 0.2Ni 0.8Al 0.0O 2Superior; (3) security performance compares LiCoO 2And LiCo 0.2Ni 0.8Al 0.0O 2Better.
Table 6 LiCoO 2: LiMn 2O 4: LiCo 0.2Ni 0.77Al 0.03O 2=A:B:C
Ternary system electrochemistry and heat release parameter
Sequence number The A:B:C mixing ratio Discharge capacity (mAh/g) Charging capacity (mAh/g) Put and fill efficient (%) Exothermic heat of reaction (J/g) Discharge capacity increases (%) Exothermic heat of reaction increases (%)
0 100:0:0 140 146 95.9 610 0 0
1 80:10:10 144 152 94.7 600 3 -2
2 60:20:20 147 157 93.6 591 5 -3
3 40:30:30 151 163 92.6 581 8 -5
4 20:40:40 154 168 91.7 572 10 -6
5 0:50:50 158 174 90.8 562 13 -8
Example six: LiCoO 2/ LiMn 2O 4/ LiCo 0.2Ni 0.75Al 0.05O 2Ternary system
The electrochemistry and the exothermic heat of reaction parameter of this ternary system have been listed in the table 7.This ternary system is similar to previous ternary system, but exothermic heat of reaction is with LiCoO 2/ LiCo 0.2Ni 0.75Al 0.05O 2The increase of solid solution, oxide and obviously reducing, the range of decrease is up to 23%, and its discharge capacity still increases by 9%.The battery product that such ternary system is had relatively high expectations to security performance, for example laptop computer and large-sized power battery are the most favourable.The best safety performance is promptly arranged, the improvement of discharge capacity is arranged again.
Table 7 LiCoO 2: LiMn 2O 4: LiCo 0.2Ni 0.75Al 0.05O 2=A:B:C
Ternary system electrochemistry and heat release parameter
Sequence number Mixing ratio Discharge capacity (mAh/g) Charging capacity (mAh/g) Put and fill efficient (%) Exothermic heat of reaction (J/g) Discharge capacity increases (%) Exothermic heat of reaction increases (%)
0 100:0:0 140 146 95.9 610 0 0
1 80:10:10 143 151 94.6 581 2 -5
2 60:20:20 145 155 93.4 553 4 -9
3 40:30:30 148 160 92.3 524 6 -14
4 20:40:40 150 165 91.3 496 7 -19
5 0:50:50 153 170 90.3 467 9 -23
Fig. 5 shows LiCoO 2/ LiMn 2O 4/ LiCo 0.2Ni 0.75Al 0.05O 2The discharge capacity of ternary system and exothermic heat of reaction are with LiMn 2O 4/ LiCo 0.2Ni 0.75Al 0.05O 2The increase of mixed oxide and present different trend with binary system.Its exothermic heat of reaction is with LiMn 2O 4/ LiCo 0.2Ni 0.8Al 0.0O 2The increase of solid solution, oxide and descending rapidly.On the contrary, discharge capacity presents more slowly increases.
Two, preparation technology
(1) do, wet and use mixing method
At first with LiCoO 2Powder is put into ball mill, presses formula rate then and adds conductive carbon powder.Do and mix after 10 minutes, press formula rate and add LiCo 0.2Ni 0.8-xAl xO 2(x=0～0.05) solid solution, oxide powder for ternary system, adds LiMn simultaneously 2O 4And then do and mixed 10 minutes.The dry mixed powder that obtains thus has than low contact resistance and high electrical conductivity, because active material surface is wherein wrapped up by conductive carbon powder.After powder behind the ball milling taken out steel ball through vibrating screen, pour in advance in the polymer solution for preparing by formula rate.At last, mixed 1 hour down at middling speed 500-800 rev/min.
(2) wet mixing method
At first polymeric binder is joined in the organic solvent, add conductive carbon powder then by formula rate.Mix after 10 minutes, press formula rate and add LiCo 0.2Ni 0.8-xAl xO 2(x=0～0.05) solid solution, oxide powder mixed 30 minutes down at middling speed 500-800 rev/min.Then, add LiCoO 2Powder for ternary system, adds LiMn simultaneously 2O 4Mixed 1 hour down at high speed 1500-1800 rev/min.The wet mixing slurry that obtains has thus kept original particle size, have good safety performance, because the powder after ball milling do to mix, its particle size may be owing to grind and external force effect such as collision and reducing greatly, superfine powder content is increased, and the electrochemical reaction of powder is active to be increased.
Three, test event and method
(1) slurry viscosity
Electrode film thickness in slurry viscosity and the coating process, density, paste quality index such as knot property with substrate closely related.Also influence technological parameters such as slurry speed, electrode film output simultaneously.For the quality that guarantees electrode slice and the consistency of battery product, before each coating, all must detect slurry.Slurry viscosity exceeds must can using after the adjustment of process viscosity of tolerance band.
Use rotation viscometer that prepared slurry is detected.Because the temperature of slurry, the rotary speed of viscosimeter influence very big to the slurry viscosity test result.Therefore, when record, the temperature of slurry, rotary speed and three data of slurry viscosity of viscosimeter all must be noted.
(2) slurry density
Slurry density is another important parameter of stock quality.Because the proportion of the various powders in the electrode prescription can differ 1～2 times, for example, the proportion of conductive carbon powder is 1.9g/cm 3, and LiCoO 2The proportion of powder is about 4.9g/cm 3Therefore, in mixed process or between the operating period, slurry can lamination occur because of specific gravity difference, and proportion is bigger sinks to the bottom, and proportion less float over the upper strata.The test of slurry density can indicate the quality of slurry mixing quality, and the uniformity that slurry mixes is directly connected to the consistency of composition, thickness and the density of electrode film.
Use hydrometer that prepared slurry is detected.Because the temperature of slurry is very big to the influence of slurry density test result.Therefore, when record, temperature and two data of slurry density of slurry all must be noted.Note the position of test simultaneously.
(3) electrode film density
Can directly extrapolate the capacitance the index whether battery that uses this electrode slice can reach designing requirement by electrode film density.
After removing the organic solvent in the electrode film totally through vacuum and heating drying, use precise electronic to claim to finish the electrode film Density Detection with accurate vernier scale.For the electrode film of double spread, electrode film density D computing formula is as follows:
D=(W Always-W SubstrateS)/[(L-l)]
W Always: the total weight of electrode film sample;
W Substrate: the aluminium substrate weight of same area;
S: sample area
L: thickness of sample
L: substrate thickness
(4) electrode film is to the subsides knotting strength of substrate
Electrode film interrelates to many technical indicators such as the subsides knotting strength of substrate and battery life, internal resistance size, efficiency for charge-discharges.The simplest method of testing is to estimate to paste the knotting strength grade relatively with the sticking daraf(reciprocal of farad) of adhesive tape.

Claims (10)

1. the positive electrode material of a lithium polymer battery, comprising active component, conductive carbon powder and polymer-binder, it is characterized in that active material is to be inserted the embedding combination of oxides and constituted binary system or ternary system by two kinds or three kinds of lithiums, described binary system component prescription is LiCoO 2+ LiCo 0.2Ni 0.8-xAl xO 2, x=0～0.10, described ternary system component prescription is LiCoO 2+ LiMn 2O 4+ LiCo 0.2Ni 0.8-xAl xO 2, x=0～0.10.
2. the positive electrode material of lithium polymer battery according to claim 1 is characterized in that, the proportioning of described binary system composition is LiCoO 2: LiCo 0.2Ni 0.8-xAl xO 2=80: 20～20: 80.
3. the positive electrode material of lithium polymer battery according to claim 1, the proportioning that it is characterized in that described ternary system composition is LiCoO 2: LiMn 2O 4: LiCo 0.2Ni 0.8-xAl xO 2=98: 1: 1～1: 98: 1～1: 1: 98.
4. according to the positive electrode material of claim 1 or 2 or 3 described lithium polymer batteries, it is characterized in that it is monomer or solid solution that described lithium is inserted the embedding oxide.
5. preparation technology according to any described anode of lithium polymer battery material among the claim 1-4, it is characterized in that the lithium of described binary system or ternary system is inserted the embedding oxide to mix with physics mode, its hybrid mode for do/wet mixing is legal.
6. the preparation technology of anode of lithium polymer battery material according to claim 5 is characterized in that described doing/wet mixing is legal to be at first with LiCoO 2Powder is put into ball mill, presses formula rate then and adds conductive carbon powder after mixing a period of time, presses formula rate again and adds LiCo 0.2Ni 0.8-xAl xO 2The solid solution, oxide powder for ternary system, adds LiMn simultaneously 2O 4Mix a period of time, behind the process of the powder behind ball milling vibrating screen taking-up steel ball, carry out wet-mixed with the organic solution of polymeric binder, last, mix the slurry that promptly obtained described battery positive electrode material in 1 hour down at middling speed 500-800 rev/min.
7. the preparation technology of any described anode of lithium polymer battery material among the claim 1-4 is characterized in that the lithium of described binary system or ternary system is inserted the embedding oxide to mix with physics mode, and its hybrid mode is that wet mixing is legal.
8. the preparation technology of anode of lithium polymer battery material according to claim 7, it is characterized in that described wet mixing legal be at first polymeric binder to be joined in the organic solvent by formula rate, add conductive carbon powder then, after mixing a period of time, press formula rate and add LiCo 0.2Ni 0.8-xAl xO 2The solid solution, oxide powder mixes down at middling speed 500-800 rev/min; Then, add LiCoO 2Powder for ternary system, adds LiMn simultaneously 2O 4, mixed 1 hour down at high speed 1500-1800 rev/min; Obtain the wet mixing slurry of battery positive electrode material thus.
9. the method for testing of any described anode of lithium polymer battery material among the claim 1-4, it is characterized in that using rotation viscometer that the slurry of the battery positive electrode material for preparing is detected, the temperature of described slurry, rotary speed and three data of slurry viscosity of viscosimeter are all noted; Use hydrometer that described slurry is detected, temperature and two data of slurry density of slurry are all noted, note the position of test simultaneously.
10. the method for testing of any described anode of lithium polymer battery material among the claim 1-4, it is characterized in that the positive electrode slurry is coated with into electrode film, with the mode of vacuum and heating drying the organic solvent in the electrode film is removed totally then, re-used precise electronic and claim to finish the electrode film Density Detection with accurate vernier scale; Estimate to paste the knotting strength grade relatively with the sticking daraf(reciprocal of farad) of adhesive tape.
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