CN101378124A - Secondary battery and anode active substance - Google Patents

Secondary battery and anode active substance Download PDF

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Publication number
CN101378124A
CN101378124A CNA2007101481865A CN200710148186A CN101378124A CN 101378124 A CN101378124 A CN 101378124A CN A2007101481865 A CNA2007101481865 A CN A2007101481865A CN 200710148186 A CN200710148186 A CN 200710148186A CN 101378124 A CN101378124 A CN 101378124A
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China
Prior art keywords
conductive agent
active material
metal oxide
specific area
positive active
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CNA2007101481865A
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（请求不公开姓名）
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Evonik China Co Ltd
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Degussa China Co Ltd
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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
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Abstract

The invention provides an active material of the anode of a secondary battery, which has good capacity in both low load and high load; the active material of the anode is composed of multiple particles of a metal oxide which forms the body of the active material, a first conductive agent which covers the surfaces of all the particles of the metal oxide, and a second conductive agent which is between the particles of the metal oxide and the specific surface area thereof is less than the first conductive agent.

Description

Secondary cell and positive active material thereof
Technical field
The present invention relates to secondary cell and positive active material thereof.
Background technology
All the time, as the positive active material of secondary cell, employing be various metal oxides, but under the situation of majority therein because the electronic conductivity of metal oxide itself is low, so the conductive agent that interpolation is made of carbon dust to metal oxide.By adding conductive agent, promote reduction reaction to applying electron conduction between each metal oxide.
Herein, as influencing one of reason of battery performance, the admixture of metal oxide and conductive agent becomes problem.That is, how high equably frequency contacts metal oxide powder with carbon material micropowder.If their contact strength descends, then produce the part that electronics can not be supplied with to the positive active material transmission fully, the result is because produce with the remaining active material of unreacted state, so the utilance of positive active material reduces.
As solution to the problems described above, for example, open the spy and to have proposed the positive active material that on manganese dioxide particle surface steeped landform has become the graphite microparticles end in clear 61-No. 214362 communiques, proposed a kind of positive active material in special fair 7-No. 36332 communiques, its size ratio with metal oxide powder and Delanium powder is set at 10 -1～10 -5, the coverage rate that covers the material with carbon element of metal oxide is set at 0.5～15%.
In addition, the spy open proposed in flat 9-No. 92265 communiques by metal oxide and cover with the thickness of 0.01 μ m～0.3 μ m this metal oxide apparent surface more than 15% and specific area at 150m 2The positive active material that the above material with carbon element of/g constitutes and contain positive active material between the carbon dust of the formation conductive agent between this positive active material.
But, research according to the inventor etc. learns, in the secondary cell that has adopted the positive active material described in above-mentioned each communique, shows the utilance of good positive active material when low load and during common load, but, be 4.0mA/cm for example in current density 2About high capacity the time, battery behaviors such as capacity are insufficient.Cause by following reason according to inferring this.
That is, because metal oxide powder is covered by the conductive agent powder, so conductivity is homogenized in whole metal oxide, so the utilization ratio height of active material, under low load, demonstrate high capacity.But, owing between the particle of each metal oxide powder, have the interface,, utilization ratio is descended so it becomes resistance when high capacity, capacity also reduces.
When secondary cell being used for for example electric automobile etc., owing to also require jumbo battery behavior with the same when the low load when high capacity, so the performance the during high capacity that improves secondary cell is absolutely necessary.
Summary of the invention
Therefore, the present invention is in view of above-mentioned aspect, and purpose is to provide a kind of positive active material that has the secondary cell of good capacity when low load and during high capacity concurrently.
The inventor etc. are conceived to: when low load, improve the utilization ratio of active material by the particle surface that covers each metal oxide with the covering conductive agent as mentioned above, thereby keep good capacity; In addition, by adding other conductive agent (below, be called add conductive agent), the conductive path that forms electronics when high capacity seeks to improve battery capacity.In addition, also considered the positive electrode active material electropolarized influence of verifying.
Usually, the covering of metal oxide being carried out with conductive agent is to adopt the mechanical energy by compression, shearing etc. to mix both, and the method that the so-called mechanical treatment (machinery merges) of surface fusion takes place a plurality of particles is carried out.In the covering that utilizes mechanical treatment to carry out, it is above and less than the particulate (being the big particle of specific area) of active material particle to cover conductive agent and must be certain certain size.
The inventor etc. have studied the covering that utilizes this mechanical treatment to carry out.Its result is illustrated at Fig. 3.Fig. 3 represents along with covering (for example, the variation of 0.5wt% as shown in FIG.～5.5wt%) and make the variation that specific area took place that is capped the metal oxide particle (mixed powder) after conductive agent covers of covering conductive agent addition on the metal oxide.Herein, the processing time of abscissa is the needed time of above-mentioned mixing.
The specific area of the conductive agent after the covering reduced with the processing time, but reached capacity in its minimizing sometime.In addition, the specific area of the conductive agent after the covering also increases with the increase that covers the conductive agent addition.In the electric polarization of the metal oxide that is capped, utilize binding agent each particle that bonds to constitute positive pole, but discoveries such as the inventor, if cover the conductive agent addition to a certain degree (for example, greater than 5wt%) more than, the specific area of the conductive agent after then covering is excessive (for example, greater than 40m 2/ g), in electrode, produce easily and peel off or defective etc.At this moment, increase binder amount and get final product, but battery capacity correspondingly reduces.
Therefore, if make the specific area of described interpolation conductive agent identical or bigger than it with the covering conductive agent, then under the situation of having added conductive agent, same with the situation that has increased the addition that covers conductive agent in fact, the specific area that produces the conductive agent after the above-mentioned covering is excessive, might produce above-mentioned peeling off or defective etc. in electrode.Therefore, for electric polarization, the specific area of preferably adding conductive agent is less than covering conductive agent.In addition, it is believed that,, can increase the particle diameter that adds conductive agent, between metal oxide particle, form the conductive path of electronics easily by making the specific area of adding conductive agent greater than covering conductive agent.
So based on above-mentioned result of study, following technological means is adopted in decision.That is, invention according to claim 1 is characterized in that, it comprises: the particle that constitutes a plurality of metal oxides of active material main body; Cover the 1st conductive agent of each particle surface of metal oxide; Between between each particle of metal oxide and specific area less than the 2nd conductive agent of the 1st conductive agent.
Thus, capacity in the time of can making low load by the 1st conductive agent is good, when high capacity, guarantee simultaneously the conductive path of electronics by the 2nd conductive agent between between metal oxide particle, its peripheral active material (metal oxide) is used, therefore can seek to improve utilization ratio, realize good capacity.In addition, because the specific area of the specific area of the 2nd conductive agent conductive agent after less than the 1st conductive agent, therefore can preventing to cover is excessive, when electric polarization, can prevent to peel off or defective etc.
Therefore, according to the present invention, can provide a kind of good capacity and positive active material of electropolarized secondary cell well of having concurrently when low load and during high capacity.Herein, about the 1st conductive agent, as mentioned above, the problem such as peel off during from mechanical treatment and electric polarization it is believed that its specific area has suitable scope.
In addition, too small about the 2nd conductive agent if its specific area is compared with the 1st conductive agent, then for example become the big conductive agent of its particle diameter, volume shared in positive active material also increases, and the amount of active material reduces, degradation under the capacity, thus efficient is poor.The 2nd conductive agent is so long as can guarantee the size of the conductive path of electronics and get final product.Therefore, about the 2nd conductive agent, it is believed that its specific area also has suitable scope.
In view of above-mentioned aspect, further carried out deep experiment repeatedly with regard to different various conductive agents such as various metal oxides and shape or materials, obtained suitable conductive agent specific area and addition for the effect that can realize aforesaid right requirement 1 described invention.So the described invention of claim 2～4 is adopted in decision.That is, invention according to claim 2 is characterized in that, the specific area of the 1st conductive agent is 250m 2/ g～1500m 2/ g, the addition Awt% with respect to metal oxide of the 1st conductive agent is 0.5wt%≤A≤5.0wt%.In addition, invention according to claim 3 is characterized in that, the specific area of the 2nd conductive agent is 1m 2/ g～200m 2/ g.
In addition, invention according to claim 4 is characterized in that, metal oxide is at least a kind that is selected from lithium manganese oxide, lithium nickel oxide, lithium and cobalt oxides and the manganese oxide; The specific area of the 1st conductive agent is 1000m 2/ g～1500m 2/ g; The specific area of described the 2nd conductive agent is 1m 2/ g～25m 2/ g; When the addition with respect to described metal oxide with respect to the addition of described metal oxide and the 1st and the 2nd conductive agent with the 1st conductive agent is set at Awt% and Bwt% respectively, have following relation:
0.5wt％≤A≤5.0wt％
2.5wt％≤B≤14.0wt％
0.5wt％≤B—A。
According to described these inventions of claim 2～4, can more stably realize and the equal effect of the described invention of described claim 1, can carry out the electric polarization of positive active material simultaneously well.In addition, studied the powder resistance of positive active material and the relation of load characteristic, the result learns that invention as claimed in claim 5 is such, if its powder resistance is 1.0 * 10 2Below the Ω, just can realize and the equal effect of the described invention of described claim 1.
In addition, invention as claimed in claim 6 is such, if make the secondary cell that possesses as any one described positive active material in the claim 1～5, just can provide to have when low load and have good capacity during high capacity concurrently, be difficult for peeling off or the secondary cell of the positive pole of defective etc. simultaneously.
Description of drawings
Fig. 1 is the general profile chart that the epithelium of expression embodiments of the present invention forms the formation of device.
Fig. 2 is the chart of the Capacity Ratio under the various additions of the conductive agent of expression in the positive active material.
Fig. 3 is that expression is covered the variation of the covering conductive agent addition on the metal oxide during along with mechanical treatment and chart that the specific area of the mixed powder after the covering is changed.
Fig. 4 is the key diagram of the effect of the conductive agent in the expression positive pole.
Fig. 5 is the chart of relation of the powder resistance of expression addition of conductive agent and positive active material.
Symbol description
1 going barrel, 2 fixed axis, 3 extrusion shearing heads, 4 the 1st arms, 5 pawls, 6 the 2nd arms, 10 inner spaces, 20 add conductive agent, 21 covers conductive agent, 22 positive active material particles, 23 collector bodies.
Embodiment
Below, in the present embodiment,, be described with the Li secondary cell as secondary cell.In the present embodiment, the metal oxide as constituting the positive active material main body can adopt lithium manganese oxide, lithium nickel oxide, lithium and cobalt oxides and manganese oxide etc.
As each particle surface that covers metal oxide and in metal oxide with the covering conductive agent (the 1st conductive agent) of the conductivity homogenizing of electronics, can adopt specific area is 250m 2/ g～1500m 2The section's qin carbon black of/g or acetylene carbon black etc.Also have, in order to improve capacity more, more preferably specific area is 1000m 2/ g～1500m 2/ g (opening Fig. 4 of flat 9-No. 92265 communiques with reference to the spy).
In addition, as the interpolation conductive agent (the 2nd conductive agent) that the metal oxide that is capped is further added, it is between between each particle of metal oxide and form the conductive path of electronics, and specific area is less than covering conductive agent (the 1st conductive agent), and it is 1m that this interpolation conductive agent can adopt specific area 2/ g～200m 2The carbon dust of/g etc.Also have, in order to improve electrode density, more preferably specific area is 1m 2/ g～25m 2About/g.
Below, an example of positive active material is described, wherein adopt LiMn as metal oxide 2O 4(average grain diameter is 7 μ m) is that 0.03 μ m, specific area are 1270m as covering conductive agent employing average grain diameter 2The Lion corporate system section qin carbon black of/g (below, be abbreviated as KB), (average grain diameter is that 3.4 μ m, specific area are 21.3m as adding conductive agent employing Lonza Japan corporate system KS-6 2/ g), and the said firm system KS-15 (average grain diameter is that 7.5 μ m, specific area are 12.8m 2/ g).Present embodiment is not limited to this example.
At LiMn 2O 4Each particle surface on cover KB mechanical treatment be with at LiMn 2O 4In mixed mixed powder that the KB of ormal weight forms and adopt the epithelium shown in Fig. 1 to form that device carries out.It is to be made of following part that this epithelium forms device: going barrel 1, and it has inner space 10; The 1st arm 4, it is fixed on the fixed axis 2 of this going barrel 1 inside and extends near the inner peripheral surface of going barrel 1, and has the extrusion shearing head 3 of semi-circular shape; The 2nd arm 6, its rear swivel at above-mentioned the 1st arm 4 is fixed on the fixed axis 2 at interval predetermined angular, and has near the pawl 5 the inner peripheral surface that extends to going barrel 1.
The described mixed powder of in this epithelium forms the inner space of device, packing into, make going barrel 1 with the regulation rotary speed rotation stipulated time (processing time), between the inner peripheral surface of going barrel 1 and extrusion shearing head 3, apply extrusion shearing power, thereafter by scraping with pawl 5 and mixing, thus at LiMn 2O 4Each particle surface on covered KB.The LiMn that is obtaining by above mechanical treatment by the KB covering 2O 4In, together add KS-6 or KS-15 with binding agent PVDF (Kynoar), add solvent (N-methyl-2-pyrrolidones etc.) again, carry out mixing and formation paste shape.Setting binding agent herein, is several % (for example about 3%).
With the scraper plate method paste that obtains is coated on the Al paper tinsel collector body, carries out drying, press forming then, make electrode (positive pole).This electrode stamping-out is become discoideus, further carry out vacuumize, move into then in the drying box, carry out the making of Coin-shaped battery.Adopt Osaka gas companies system MCMB (mesophase-carbon micro-beads grain), barrier film to adopt eastern burning length of schooling Tapyrus25 μ m, electrolyte to adopt the LiPF of 1M to electrode (negative pole) 6/ EC (50) DME (50) has promptly dissolved the LiPF of 1M in the solvent that has mixed EC (ethylene carbonate) and DME (dimethoxy-ethane) respectively with 50 capacity % 6And the electrolyte that obtains.
Appreciation condition is: charging is 4.2V * 5h, 1.0mA/cm 2, CC/CV condition; Discharge is that 3.0V disconnects CC.In the table of Fig. 2, being illustrated in discharge current density is 4.0mA/cm 2The time, i.e. the positive electrode capacity of the various positive active materials of this example during high capacity is than (below, be called Capacity Ratio).The chart of Fig. 2 is that expression will be with respect to LiMn 2O 4KB amount, total conduction dosage (each wt%) of having added KS-15 or at KS-6 o'clock carry out various variations and the Capacity Ratio that obtains.Herein, described KB amount is equivalent to cover the addition Awt% with respect to metal oxide of conductive agent (the 1st conductive agent), and described total conduction dosage is equivalent to the total addition Bwt% with respect to metal oxide of two conductive agents.
Described KB amount is with LiMn 2O 4KB amount when the summation of amount and KB amount is set at 100wt%, left column is represented 0wt%, 0.5wt%, 1.5wt%, 2.5wt%, 3.5wt%, 4.0wt% in the chart.In addition, described total conduction dosage is with LiMn 2O 4KB amount and KS-15 measured the total addition of (or KS-6 measures) when the summation of amount, KB amount, KS-15 amount (or KS-6 amount) and binding agent (PVDF) was set at 100wt%, and epimere is represented from 1.5wt% to 10.0wt% in the chart.
Herein, because KB amount is good capacity for 0wt%, the KS-15 that adds 10wt% or KS-6 o'clock capacity, be 1 to represent Capacity Ratio therefore with the capacity of this moment.So, for example, KB amount for 1.5wt%, always conduct electricity dosage when being 2.5wt% the Capacity Ratio of (KS-15 amount is 1.0wt%) be expressed as 1.04.From this chart as can be known, show good capacity be Capacity Ratio more than 1 (among Fig. 2, the value that with dashed lines fences up) is, KB amount (A) is 0.5wt%≤A, total conduction dosage (B) be 2.5wt%≤B, and deducts that KB measures (A) and the value B-A that obtains is B-A 〉=0.5wt% from total conduction dosage (B).Additional disclosure when B-A＜0.5wt%, promptly in the amount of KS-15 or KS-6 after a little while, can not obtain good Capacity Ratio once.
In addition, if (0.5mA/cm during to low load 2) also study capacity, then can learn, when the total amount that covers and add conductive agent when 15wt% is above, because LiMn 2O 4Amount descend, the capacity during load reduces, and is therefore not preferred.So the total amount (always conduct electricity dosage Bwt%) that covers and add conductive agent preferably sets at 2.5wt%≤B≤14.0wt%.
In addition, as described shown in Figure 3 in the summary of the invention part, for electric polarization, the addition that covers conductive agent and be KB (covering conductive agent) is preferably below 5.0wt%.Also have, among Fig. 3, the processing time of abscissa is described mechanical treatment time (unit: minute), and ordinate is at LiMn 2O 4Specific area (the unit: m of the mixed powder behind the last covering KB 2/ g), each graphic indicia is corresponding with each addition of KB.And, if the addition of KB greater than 5.0wt%, then because of specific area greater than 40m 2/ g peels off or defective etc. and produce at electrode easily.
If the experience based on the addition of relevant these each conductive agents then can draw to draw a conclusion.That is, about KB (covering conductive agent), with respect to LiMn 2O 4Addition (KB measures Awt%) be preferably 0.5wt%≤A≤5.0wt%, the total addition (always conduct electricity dosage Bwt%) that covers and add conductive agent is preferably 2.5wt%≤B≤14.0wt%.
So, as positive active material, the particle that comprises a plurality of metal oxides that constitute the active material main body by employing, cover each particle surface of metal oxide and in metal oxide with the covering conductive agent of the conductivity homogenizing of electronics, the specific area of conductive path that forms electronics between between each particle of metal oxide and in high capacity the time is less than the positive active material of the interpolation conductive agent that covers conductive agent, have good capacity in the time of can being provided at low load and during high capacity concurrently, positive active material that simultaneously can electropolarized well Li secondary cell.
Wherein, can infer, the mechanism that can have good capacity when low load and during high capacity concurrently is as follows.Action Specification figure with reference to the conductive agent of the positive pole of Fig. 4 describes.Among Fig. 4,20 be that positive active material particle (below, be called active material), 23 is a collector body for adding conductive agent, 21 for covering conductive agent, 22.And, (a) be to have only to add conductive agent 20 and be included in situation in the active material 22, (b) being to have only to cover conductive agent 21 and be included in situation in the active material 22, (c) is to cover conductive agent 21 and add conductive agent 20 that both all are included in situation in the active material 22.
When hanging down load, in the electrode of (a),, therefore the active material 22 of the conductivity of can not get is arranged owing to have the gap 22 at active material more, can not produce sufficient capacity.In the electrode of (b), owing to obtain conductivity equably by covering conductive agent 21, thereby the utilization ratio height of active material 22, capacity increases.When high capacity, in the electrode of (a), exist because of adding conductive agent 20 parts, and on this part, form the very conductive path of good electron of conductivity, near the active material 22 it has been used.Therefore, capacity increases.In the electrode of (b), owing to have the interface,, utilization ratio is descended so can think that these interfaces become resistance 22 of each active materials, capacity reduces.
On the other hand, in the electrode of (c),,, can have good capacity concurrently so when low load and high capacity, all can improve the utilization ratio of active material 22 owing to be the combination of described (a) and electrode (b)., study powder resistance, obtain result shown in Figure 5 for each positive active material that the mix proportion in the chart of described Fig. 2 has taken place to change.
Fig. 5 represents the covering in the positive active material and adds the total addition (adding up to conduction dosage) of conductive agent and the chart of the relation of the powder resistance of positive active material.Ordinate is represented powder resistance (Ω).In addition, abscissa is total conduction dosage (wt%), but to from a left side being 10.0wt%, 2.5wt%, these 4 kinds of situations of 4.5wt%, 6.5wt% in order, demarcates at vertical with dashed lines.
And, adding up in the zone of conduction dosage at each, the numerical value shown in chart is interior is KB amount (wt%), with the mapping from left to right in order of KB amount mode from small to large.Also have, total conduction dosage is that the diagram in the zone of 10.0wt% is that the KB amount is 0wt%, promptly without mechanical treatment.In addition, among the figure, represents to contain KS-6 and KB, and ◇ represents to contain KS-15 and KB.Therefore, for example, be in the zone of 6.5wt% adding up to conduction dosage, the most left is that powder resistance is approximately 1.0 * 10 2Ω, but at this moment, KB is 0.5wt%, and KS-6 is 6.0wt%.
As can be seen from Figure 5, being positioned at powder resistance at the conductive agent of capacity good shown in the chart of Fig. 2 is 1.0 * 10 2The zone that Ω is following.In other words, need only powder resistance 1.0 * 10 2Below the Ω, just can improve load characteristic.It is believed that this is because improved the cause of the electron conduction of active material.More than, with the above-mentioned example present embodiment that has been base description, but so long as each metal oxide described in the present embodiment, cover conductive agent, add conductive agent, just can obtain the effect equal with this example.

Claims (6)

1. the positive active material of a secondary cell is characterized in that, comprises:
Constitute the particle of a plurality of metal oxides of active material main body;
Cover the 1st conductive agent of each particle surface of described metal oxide; With
Between between each particle of described metal oxide and specific area less than the 2nd conductive agent of described the 1st conductive agent.
2. the positive active material of secondary cell as claimed in claim 1 is characterized in that, the specific area of described the 1st conductive agent is 250m 2/ g～1500m 2/ g, described the 1st conductive agent with respect to the addition Awt% of described metal oxide in following scope: 0.5wt%≤A≤5.0wt%.
3. the positive active material of secondary cell as claimed in claim 1 is characterized in that, the specific area of described the 2nd conductive agent is 1m 2/ g～200m 2/ g.
4. the positive active material of secondary cell as claimed in claim 1 is characterized in that,
Described metal oxide is at least a kind that is selected from lithium manganese oxide, lithium nickel oxide, lithium and cobalt oxides and the manganese oxide;
The specific area of described the 1st conductive agent is 1000m 2/ g～1500m 2/ g, the specific area of described the 2nd conductive agent is 1m 2/ g～25m 2/ g;
Described the 1st conductive agent have following relation with respect to the addition Awt% of described metal oxide and the total addition Bwt% with respect to described metal oxide of described two conductive agents:
5wt％≤A≤5.0wt％
2.5wt％≤B≤14.0wt％
5wt％≤B—A。
5. as the positive active material of any one described secondary cell in the claim 1～4, it is characterized in that powder resistance is 1.0 * 10 2Below the Ω.
6. a secondary cell is characterized in that, possesses any one described positive active material in the claim 1～5.
CNA2007101481865A 2007-08-28 2007-08-28 Secondary battery and anode active substance Pending CN101378124A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108292738A (en) * 2015-12-09 2018-07-17 住友电气工业株式会社 Sodium ion secondary battery and positive active material particle
CN109920979A (en) * 2017-12-12 2019-06-21 宁德时代新能源科技股份有限公司 Positive plate and electrochemical cell

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108292738A (en) * 2015-12-09 2018-07-17 住友电气工业株式会社 Sodium ion secondary battery and positive active material particle
CN108292738B (en) * 2015-12-09 2021-01-12 住友电气工业株式会社 Sodium ion secondary battery and positive electrode active material particle
CN109920979A (en) * 2017-12-12 2019-06-21 宁德时代新能源科技股份有限公司 Positive plate and electrochemical cell

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